Food and flavorant compositions comprising renewably-based, biodegradable 1,3-propanediol

ABSTRACT

Disclosed herein are food and flavorant compositions comprising 1,3-propanediol, wherein the 1,3-propanediol in said compositions has a bio-based carbon content of about 1% to 100%. In addition, it is preferred that the 1,3-propanediol be biologically-derived, and wherein upon biodegradation, the biologically-derived 1,3-propanediol contributes no anthropogenic CO 2  emissions to the atmosphere.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 11/705,254 filed Feb. 12, 2007, which claims thebenefit of U.S. Provisional Application Ser. No. 60/772,471, filed Feb.10, 2006; U.S. Provisional Application No. 60/772,194, filed Feb. 10,2006, U.S. Provisional Application No. 60/772,193, filed Feb. 10, 2006,U.S. Provisional Application No. 60/772,111, filed Feb. 10, 2006, U.S.Provisional Application No. 60/772,120, filed Feb. 10, 2006, U.S.Provisional Application No. 60/772,110, filed Feb. 10, 2006, U.S.Provisional Application No. 60/772,112, filed Feb. 10, 2006, U.S.Provisional Application No. 60/846,948, filed Sep. 25, 2006, U.S.Provisional Application No. 60/853,920, filed Oct. 24, 2006, U.S.Provisional Application No. 60/859,264, filed Nov. 15, 2006, U.S.Provisional Application No. 60/872,705, filed Dec. 4, 2006 and U.S.Provisional Application No. 60/880,824, filed Jan. 17, 2007, thedisclosures of which are expressly incorporated herein by reference intheir entirety.

FIELD OF THE INVENTION

Disclosed herein are biodegradable compositions comprising1,3-propanediol wherein the 1,3-propanediol in said biodegradablecomposition has a bio-based carbon content of about 1% to 100%. Inaddition, it is preferred that the 1,3-propanediol bebiologically-derived, and wherein upon biodegradation, thebiologically-derived 1,3-propanediol contributes no anthropogenic CO₂emissions to the atmosphere.

BACKGROUND OF THE INVENTION

Consumers of biodegradable products, such as personal care, cosmeticsand detergents, among many others, consider many factors in selectingproducts for use. Recently certain factors have been a focus of and havedriven scientific study and product development. These driving factorsinclude, product safety, environmental impact, the extent to which thecomponents are natural, and the aesthetic quality of the overallproduct. Therefore, manufacturers have to be concerned with theenvironmental impact of their products. In fact, the effort towardsenvironmental impact awareness is a universal concern, recognized bygovernment agencies. The Kyoto Protocol amendment to the United NationsFramework Convention on Climate Change (UNFCCC) currently signed by 156nations is one example of a global effort to favor safer environmentalmanufacturing over cost and efficiency. When applied to biodegradableproducts, consumers are increasingly selective about the origins of theproducts they purchase. The 2004 Co-operative Bank's annual EthicalConsumerism Report (www.co-operativebank.co.uk) disclosed a 30.3%increase in consumer spending on ethical retail products (a generalclassification for environmental safe, organic and fair trade goods)between 2003 and 2004 while total consumer spending during the sameperiod rose only 3.7%.

Glycols such as ethylene glycol, propylene glycol, 1,3-butylene glycol,and 2-methyl-1,3-propanediol are biodegradable compounds useful incompositions ranging from cosmetics and personal care formulations todetergents to heat transfer compositions. While biodegradability is animportant factor in protecting the environment, biodegradation ofglycols derived from fossil-based sources has the unavoidableconsequence of releasing previously fixed CO2 into the atmosphere. Thus,while glycols in general are advantageous for their biodegradability,the resulting global warming potential of fossil-based glycols duringbiodegradation is significant.

Carbon dioxide is singled out as the largest component of the collectionof greenhouse gases in the atmosphere. The level of atmospheric carbondioxide has increased 50% in the last two hundred years. Recent reportsindicate that the current level of atmospheric carbon dioxide is higherthan the peak level in the late Pleistocene, the epoch before modernhumans (Siegenthaler, U. et al. Stable Carbon Cycle-Climate RelationshipDuring the Late Pleistocene, Science, Vol. 310, no. 5752 (Nov. 25,2005), pp. 1313-1317). Therefore, any further addition of carbon dioxideto the atmosphere is thought to further shift the effect of greenhousegases from stabilization of global temperatures to that of heating.Consumers and environmental protection groups alike have identifiedindustrial release of carbon into the atmosphere as the source of carboncausing the greenhouse effect.

Greenhouse gas emission can occur at any point during the lifetime of aproduct. Consumers and environmental groups consider the full lifespanof a product when evaluating a product's environmental impact. Consumerslook for products that do not contribute new carbon to the atmosphereconsidering the environmental impact of production, use and degradation.Only organic products composed of carbon molecules from plant sugars andstarches and ultimately atmospheric carbon are considered to not furthercontribute to the greenhouse effect.

In addition to adding carbon dioxide to the atmosphere, current methodsof industrial production of glycols produce contaminants and wasteproducts that include among them sulfuric acid, hydrochloric acid,hydrofluoric acid, phosphoric acid, oxalic acid tartaric acid, aceticacids, Alkali metals, alkaline earth metals, transitional metals andheavy metals, including Iron, cobalt, nickel, copper, silver,molybdenum, tungsten, vanadium, chromium, rhodium, palladium, osmium,iridium, rubidium, and platinum (U.S. Pat. Nos. 2,434,110, 5,034,134,5,334,778, and 5,10,036).

Also of concern to consumers of biodegradable products, especiallyconsumers of personal care, cosmetics and detergent products, is anindividual's reaction to such a product. The rate of development ofhypersensitivity has markedly increased in the US in the last twodecades. Many of these reactions are attributed to trace amount ofsubstances. Other reactions are of idiopathic origin. Consumers seekproducts that are composed of ingredients of a more purified sourceand/or of all natural composition.

SUMMARY OF THE INVENTION

The present invention is directed to a biodegradable compositioncomprising 1,3-propanediol and an ingredient, wherein said1,3-propanediol has a bio-based carbon content of at least 1%.

The present invention is further directed to a biodegradable compositioncomprising 1,3-propanediol and an ingredient wherein the ingredient isselected from the group consisting of an acceptable carrier, an active,water, an aqueous solution, a surfactant, a builder, a pH control agent,a corrosion inhibitor, a defoamer, a dye and a food ingredient, andwherein said 1,3-propanediol has a bio-based carbon content of at least1%.

The present invention is even further directed to a biodegradablecomposition comprising 1,3-propanediol and an ingredient, and furthercomprising a composition selected from the group consisting of apersonal care product, a cosmetic, a detergent, a heat transfercomposition, a deicing composition, a food, a paint, and an ink, whereinsaid 1,3-propanediol has a bio-based carbon content of at least 1%.

The present invention is also directed to a biodegradable compositioncomprising 1,3-propanediol wherein said 1,3-propanediol has anultraviolet absorption at 220 nm of less than about 0.200 and at 250 nmof less than about 0.075 and at 275 nm of less than about 0.075.

The present invention is additionally directed to a biodegradablecomposition comprising 1,3-propanediol wherein said 1,3-propanediol hasa concentration of total organic impurities of less than about 400 ppm.

The present invention is even further directed to a biodegradablecomposition comprising 1,3-propanediol, wherein the 1,3-propanediol insaid composition has an anthropogenic CO₂ emission profile of zero uponbiodegradation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing CO₂ emissions for CO₂ fixation from theatmosphere during photosynthesis for renewably based 1,3-propanediol(Bio-PDO™) (−1.7 kg CO₂/kg product) and CO₂ release to the atmosphereduring biodegradation (kg CO₂/kg product) for ethylene glycol (EG) (+1.4kg CO₂/kg product), propylene glycol (PG) (+1.7 kg CO₂/kg product),fossil-based 1,3-propanediol (Chem-PDO) (+1.7 kg CO₂/kg product), andfermentatively-derived 1,3-propanediol (Bio-PDO™) (+1.7 kg CO₂/kgproduct).

FIG. 2 is a graph showing that the net emissions of CO₂ to theatmosphere for renewably based 1,3-propanediol (Bio-PDO) is zero (0).

FIG. 3 is a table that shows the calculations for the data shown inFIGS. 1 and 2.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Compositions disclosed herein comprise 1,3-propanediol, having at least1% bio-based carbon content, as greater as up to 100% of the glycolcomponent of the composition. In one embodiment, the 1,3-propanediolcomprises substantially all of the glycol component of the compositionof the invention. In another embodiment, the 1,3-propanediol comprisesall of the glycol component of the composition.

1,3-Propanediol

The terms “bioPDO”, “biologically-derived, biodegradable1,3-propanediol”, “biologically derived 1,3-propanediol”,“renewably-based 1,3-propanediol”, “renewably-based, biodegradable1,3-propanediol,” “biosourced, and “biologically-produced1,3-propanediol” and similar terms as used here in refer to1,3-propanediol derived from microorganism metabolism of plant-derivedsugars composed of carbon of atmospheric origin, and not composed offossil-fuel carbon.

Anthropogenic CO₂ Emission Profile

Applicants' invention relates to biodegradable compositions, such as,among many others, personal care products, cosmetics, detergents, heattransfer fluids, deicing fluids, foods, paints and inks, comprisingrenewably-based, biodegradable 1,3-propanediol, in which saidrenewably-based, biodegradable 1,3-propanediol has an anthropogenic CO₂emission profile of zero (0). An “anthropogenic emission profile” meansanthropogenic CO2 emissions that are contributed to the atmosphere uponbiodegradation of a compound or composition. p

“Biodegradable” or “Biodegradability” means the capacity of a compoundto be broken down by living organisms to simple, stable compounds suchas carbon dioxide and water.

Whereas photosynthesis is the process of creating growing matter throughthe conversion of carbon dioxide (CO₂) and water (H₂O) into plantmaterial through the action of the sun, biodegradation is the process ofconverting organic material back into CO₂ and H₂O through the activityof living organisms.

There are many published test methods for measuring the biodegradabilityof organic chemicals such as glycols. One internationally recognizedmethod is ASTM E1720-01, Standard Test Method for Determining Ready,Ultimate Biodegradability of Organic Chemicals in a Sealed Vessel CO₂Production Test.

Chemicals that demonstrate 60% biodegradation or better in this testmethod will biodegrade in most aerobic environments and are classifiedas ready biodegradable. All of the glycols referred to in this documentmeet this criteria.

Calculations setting forth the finding that the 1,3-propanediol of thepresent invention provides no anthropogenic COs emissions uponbiodegradation is set forth below. A table in support of thesecalculations is provided in FIG. 3.

When one molecule of 1,3-propanediol degrades, three molecules of CO₂are released into the atmosphere. Because all of these molecules of CO₂released during degradation from “fermentatively-derived”1,3-propanediol have an atmospheric origin, the net release of CO₂ tothe atmosphere is thus zero. Comparatively, because a fossilfuel-derived propylene glycol and fossil-derived 1,3-propanediolcontains three carbon atoms which originate from a fixed carbon source(i.e., the fossil fuel), degradation of one molecule of fossilfuel-derived propylene glycol or 1,3-propanediol results in a netrelease of three molecules of CO₂ into the atmosphere. Similarly,because fossil fuel-derived ethylene glycol contains two carbon atoms,which originate from a fixed carbon source, degradation of one moleculeof fossil fuel-derived ethylene glycol results in a net release of twomolecules of CO₂ into the atmosphere.

In order to quantify the CO₂ released for one kilogram of each ethyleneglycol, propylene glycol, chemical 1,3-propanediol and“fermentatively-derived” 1,3 propanediol (Bio-PDO™), the product weight(1 kg) is divided by its molecular weight. For each carbon atom presentin the molecule, one molecule of CO₂ is released. The molecules of CO₂are multiplied by the molecular weight of CO₂ (44 kg/kmole) to quantifythe impact of CO₂ release (kg) per one unit (kg) of product.

Fossil-Fuel Based Carbon Feedstock Release

1 kg of fossil fuel derived ethylene glycol*(1 kmol EG/62.068 kg)*(2kmol CO₂/1 kmol EG)*(44 kg CO₂/kmol CO₂)=1.4 kg CO₂

1 kg of fossil fuel derived propylene glycol*(1 kmol PG/76.094 kg)*(3kmol CO₂/1 kmol PG)*(44 kg CO₂/kmol CO₂)=1.7 kg CO₂

1 kg of fossil fuel derived 1,3-propanediol*(1 kmol chem-PDO/76.094kg)*(3 kmol CO₂/1 kmol chem-PDO)*(44 kg CO₂/kmol CO₂)=1.7 kg CO₂

Bio-Based Carbon Feedstock Balance

Capture:

1 kg of Bio-PDO™*(1 kmol Bio-PDO™/76.094 kg)*(−3 kmol CO₂/1 kmolBio-PDO™)*(44 kg CO₂/kmol CO₂)=−1.7 kg CO₂

Release:

1 kg of Bio-PDO™*(1 kmol Bio-PDO™/76.094 kg)*(3 kmol CO₂/1 kmolBio-PDO™)*(44 kg CO₂/kmol CO₂)=1.7 kg CO₂

Net:

−1.7 kg+1.7 kg=0 kg

This Bio-based Carbon Feedstock Balance result demonstrates that thereare no anthropogenic CO2 emissions from the biodegradation of therenewably sourced Bio-PDO. The term “anthropogenic” means man-made orfossil-derived.

Bio-Based Carbon

“Carbon of atmospheric origin” as used herein refers to carbon atomsfrom carbon dioxide molecules that have recently, in the last fewdecades, been free in the earth's atmosphere. Such carbons in mass areidentifiable by the present of particular radioisotopes as describedherein. “Green carbon”, “atmospheric carbon”, “environmentally friendlycarbon”, “life-cycle carbon”, “non-fossil fuel based carbon”,“non-petroleum based carbon”, “carbon of atmospheric origin”, and“biobased carbon” are used synonymously herein.

“Carbon of fossil origin” as used herein refers to carbon ofpetrochemical origin. Such carbon has not been exposed to UV rays asatmospheric carbon has, therefore masses of carbon of fossil origin hasfew radioisotopes in their population. Carbon of fossil origin isidentifiable by means described herein. “Fossil fuel carbon”, “fossilcarbon”, “polluting carbon”, “petrochemical carbon”, “petro-carbon” andcarbon of fossil origin are used synonymously herein.

The abbreviation “IRMS” refers to measurements of CO2 by high precisionstable isotope ratio mass spectrometry.

The term “carbon substrate” means any carbon source capable of beingmetabolized by a microorganism wherein the substrate contains at leastone carbon atom.

“Renewably-based” denotes that the carbon content of the 1,3-propanediolis from a “new carbon” source as measured by ASTM test method D 6866-05Determining the Biobased Content of Natural Range Materials UsingRadiocarbon and Isotope Ratio Mass Spectrometry Analysis, incorporatedherein by reference. This test method measures the C-14/C-12 isotoperatio in a sample and compares it to the C-14/C-12 isotope ratio in astandard 100% biobased material to give percent biobased content of thesample. “Biobased materials” are organic materials in which the carboncomes from recently (on a human time scale) fixated CO₂ present in theatmosphere using sunlight energy (photosynthesis). On land, this CO₂ iscaptured or fixated by plant life (e.g., agricultural crops or forestrymaterials). In the oceans, the CO₂ is captured or fixated byphotosynthesizing bacteria or phytoplankton. A biobased material has aC-14/C-12 isotope ratio in range of from 1:0 to greater than 0:1.Contrarily, a fossil-based material, has a C-14/C-12 isotope ratio of0:1.

A small amount of the carbon dioxide in the atmosphere is radioactive.This 14C carbon dioxide is created when nitrogen is struck by anultra-violet light produced neutron, causing the nitrogen to lose aproton and form carbon of molecular weight 14 which is immediatelyoxidized in carbon dioxide. This radioactive isotope represents a smallbut measurable fraction of atmospheric carbon. Atmospheric carbondioxide is cycled by green plants to make organic molecules during theprocess known as photosynthesis. The cycle is completed when the greenplants or other forms of life metabolize the organic molecules producingcarbon dioxide which is released back to the atmosphere. Virtually allforms of life on Earth depend on this green plant production of organicmolecule to produce the chemical energy that facilitates growth andreproduction. Therefore, the 14C that exists in the atmosphere becomespart of all life forms, and their biological products. These renewablybased organic molecules that biodegrade to CO2 do not contribute toglobal warming as there is no net increase of carbon emitted to theatmosphere. In contrast, fossil fuel based carbon does not have thesignature radiocarbon ratio of atmospheric carbon dioxide.

Atmospheric origin and fixed carbon source as used herein are relativeterms in that the time period of when CO2 is of atmospheric or fixedorigin relates to the life cycle of the 1,3-propanediol. Thus, while itis quite possible that, at one time, carbon from a fossil fuel was foundin the atmosphere (and, as a corollary, that atmospheric CO2 may one daybe incorporated into a fixed carbon source), for purposes herein carbonis considered to be from a fixed carbon source until it is released intothe atmosphere by degradation.

Assessment of the renewably based carbon in a material can be performedthrough standard test methods. Using radiocarbon and isotope ratio massspectrometry analysis, the biobased content of materials can bedetermined. ASTM International, formally known as the American Societyfor Testing and Materials, has established a standard method forassessing the biobased content of materials. The ASTM method isdesignated ASTM-D6866.

The application of ASTM-D6866 to derive a “biobased content” is built onthe same concepts as radiocarbon dating, but without use of the ageequations. The analysis is performed by deriving a ratio of the amountof radiocarbon (14C) in an unknown sample to that of a modem referencestandard. The ratio is reported as a percentage with the units “pMC”(percent modern carbon). If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount of Biomassmaterial present in the sample.

The modern reference standard used in radiocarbon dating is a NIST(National Institute of Standards and Technology) standard with a knownradiocarbon content equivalent approximately to the year AD 1950. AD1950 was chosen since it represented a time prior to thermo-nuclearweapons testing which introduced large amounts of excess radiocarboninto the atmosphere with each explosion (termed “bomb carbon”). The AD1950 reference represents 100 pMC.

“Bomb carbon” in the atmosphere reached almost twice normal levels in1963 at the peak of testing and prior to the treaty halting the testing.Its distribution within the atmosphere has been approximated since itsappearance, showing values that are greater than 100 pMC for plants andanimals living since AD 1950. It's gradually decreased over time withtoday's value being near 107.5 pMC. This means that a fresh biomassmaterial such as corn could give a radiocarbon signature near 107.5 pMC.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming 107.5pMC represents present day biomass materials and 0 pMC representspetroleum derivatives, the measured pMC value for that material willreflect the proportions of the two component types. A material derived100% from present day soybeans would give a radiocarbon signature near107.5 pMC. If that material was diluted with 50% petroleum derivatives,it would give a radiocarbon signature near 54 pMC.

A biomass content result is derived by assigning 100% equal to 107.5 pMCand 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC willgive an equivalent biobased content result of 93%.

A sample of “fermentatively-derived” 1,3-propanediol was submitted byDuPont to Iowa State University for biobased content analysis using ASTMmethod D 6866-05. The results received from Iowa State Universitydemonstrated that the above sample was 100% bio-based content (ref:Norton, Glenn. Results of Radiocarbon Analyses on samples from DuPontBio-Based Materials—reported 07-08-05).

Assessment of the materials described herein were done in accordancewith ASTM-D6866. The mean values quoted in this report encompasses anabsolute range of 6% (plus and minus 3% on either side of the biobasedcontent value) to account for variations in end-component radiocarbonsignatures. It is presumed that all materials are present day or fossilin origin and that the desired result is the amount of biobasedcomponent “present” in the material, not the amount of biobased material“used” in the manufacturing process.

Results of Radiocarbon Analyses on Samples from DuPont Bio-BasedMaterials Reported 07-08-05 PRODUCT BIOBASED CONTENT (%) 1,3-Propanediol100

There may be certain instances wherein a biodegradable composition ofthe invention may comprise a combination of a biologically-derived1,3-propanediol and one or more non biologically-derived glycolcomponents, such as, for example, chemically synthesized1,3-propanediol. In such occasions, it may be difficult, if notimpossible to determine which percentage of the glycol composition isbiologically-derived, other than by calculating the bio-based carboncontent of the glycol component. In this regard, in the biodegradablecompositions of the invention, the glycol component, and in particular,the 1,3-propanediol, can comprise at least about 1% bio-based carboncontent up to 100% bio-based carbon content, and any percentagetherebetween.

Purity

“Substantially purified,” as used by applicants to describe thebiologically-produced 1,3-propanediol produced by the process of theinvention, denotes a composition comprising 1,3-propanediol having atleast one of the following characteristics: 1) an ultraviolet absorptionat 220 nm of less than about 0.200 and at 250 nm of less than about0.075 and at 275 nm of less than about 0.075; or 2) a composition havingL*a*b* “b*” color value of less than about 0.15 and an absorbance at 270nm of less than about 0.075; or 3) a peroxide composition of less thanabout 10 ppm; or 4) a concentration of total organic impurities of lessthan about 400 ppm.

A “b*” value is the spectrophotometrically determined “Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290.

The abbreviation “AMS” refers to accelerator mass spectrometry.

By the acronym “NMR” is meant nuclear magnetic resonance.

By the terms “color” and “color bodies” is meant the existence ofvisible color that can be quantified using a spectrocolorimeter in therange of visible light, using wavelengths of approximately 400-800 nm,and by comparison with pure water. Reaction conditions can have animportant effect on the nature of color production. Examples of relevantconditions include the temperatures used, the catalyst and amount ofcatalyst. While not wishing to be bound by theory, we believe colorprecursors include trace amounts of impurities comprising olefinicbonds, acetals and other carbonyl compounds, peroxides, etc. At leastsome of these impurities may be detected by such methods as UVspectroscopy, or peroxide titration.

“Color index” refers to an analytic measure of the electromagneticradiation-absorbing properties of a substance or compound.

Biologically-derived 1,3-propanediol useful in personal care andcosmetic compositions disclosed herein has at least one of the followingcharacteristics: 1) an ultraviolet absorption at 220 nm of less thanabout 0.200 and at 250 nm of less than about 0.075 and at 275 nm of lessthan about 0.075; or 2) a composition having L*a*b* “b*” color value ofless than about 0.15 and an absorbance at 270 nm of less than about0.075; or 3) a peroxide composition of less than about 10 ppm; or 4) aconcentration of total organic impurities of less than about 400 ppm. A“b*” value is the spectrophotometrically determined Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290.

The level of 1,3-propanediol purity can be characterized in a number ofdifferent ways. For example, measuring the remaining levels ofcontaminating organic impurities is one useful measure.Biologically-derived 1,3-propanediol can have a purity level of lessthan about 400 ppm total organic contaminants; preferably less thanabout 300 ppm; and most preferably less than about 150 ppm. The term ppmtotal organic purity refers to parts per million levels ofcarbon-containing compounds (other than 1,3-propanediol) as measured bygas chromatography.

Biologically-derived 1,3-propanediol can also be characterized using anumber of other parameters, such as ultraviolet light absorbance atvarying wavelengths. The wavelengths 220 nm, 240 nm and 270 nm have beenfound to be useful in determining purity levels of the composition.Biologically-derived 1,3-propanediol can have a purity level wherein theUV absorption at 220 nm is less than about 0.200 and at 240 nm is lessthan about 0.075 and at 270 nm is less than about 0.075.

Biologically-derived 1,3-propanediol can have a b* color value (CIEL*a*b*) of less than about 0.15.

The purity of biologically-derived 1,3-propanediol compositions can alsobe assessed in a meaningful way by measuring levels of peroxide.Biologically-derived 1,3-propanediol can have a concentration ofperoxide of less than about 10 ppm.

It is believed that the aforementioned purity level parameters forbiologically-derived and purified 1,3-propanediol (using methods similaror comparable to those disclosed in U.S. Patent Application No.2005/0069997) distinguishes such compositions from 1,3-propanediolcompositions prepared from chemically purified 1,3-propanediol derivedfrom petroleum sources, as per the prior art.

Fermentation

“Biologically produced” means organic compounds produced by one or morespecies or strains of living organisms, including particularly strainsof bacteria, yeast, fungus and other microbes. “Bio-produced” andbiologically produced are used synonymously herein. Such organiccompounds are composed of carbon from atmospheric carbon dioxideconverted to sugars and starches by green plants.

“Biologically-based” means that the organic compound is synthesized frombiologically produced organic components. It is further contemplatedthat the synthesis process disclosed herein is capable of effectivelysynthesizing other monoesters and diesters from bio-produced alcoholsother than 1,3-propanediol; particularly including ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylenediol, tripropylene diol, 2-methyl 1,3-propanediol, neopentyl glycol andbisphenol A. “Bio-based”, and “bio-sourced”; “biologically derived”; and“bio-derived” are used synonymously herein.

“Fermentation” as used refers to the process of metabolizing simplesugars into other organic compounds. As used herein fermentationspecifically refers to the metabolism of plant derived sugars, suchsugar are composed of carbon of atmospheric origin.

Biologically-derived 1,3-propanediol can be obtained based upon use ofthe fermentation broth (“fermentatively-derived”) generated by agenetically-engineered Eschericia coli (E. coli) previously disclosedin, for example, U.S. Pat. No. 5,686,276. However, other singleorganisms, or combinations of organisms, may be used to biologicallyproduce 1,3-propanediol, using organisms that have beengenetically-engineered according to methods known in the art.“Fermentation” refers to a system that catalyzes a reaction betweensubstrate(s) and other nutrients to product(s) through use of abiocatalyst. The biocatalysts can be a whole organism, an isolatedenzyme, or any combination or component thereof that is enzymaticallyactive. Fermentation systems useful for producing and purifyingbiologically-derived 1,3-propanediol are disclosed in, for example,Published U.S. Patent Application No. 2005/0069997 incorporated hereinby reference.

The biologically derived 1,3-propanediol for use in the currentinvention, produced by the process described herein, contains carbonfrom the atmosphere incorporated by plants, which compose the feedstockfor the production of Bio-PDO. In this way, the Bio-PDO used in thecompositions of the invention contains only renewable carbon, and notfossil fuel based, or petroleum based carbon. Therefore the compositionsof the invention have less impact on the environment as the propanediolused in the compositions does not deplete diminishing fossil fuels and,upon degradation releases carbon back to the atmosphere for use byplants once again. Thus, the present invention can be characterized asmore natural and having less environmental impact than similarcompositions comprising petroleum based glycols.

Moreover, as the purity of the Bio-PDO utilized in the compositions ofthe invention is higher than chemically synthesized 1,3-propanediol andother glycols, risk of introducing impurities that may cause irritationis reduced by its use over commonly used glycols, such as propyleneglycol.

This 1,3-propanediol of the invention can be isolated from thefermentation broth and is incorporated into personal care and cosmeticcompositions of the invention, by processes as are known to those ofordinary skill in the applicable art.

Renewably-Based, Biodegradable 1,3-Propanediol-Containing Compositions

As mentioned above, 1,3-propanediol can be incorporated into numerouscompositions as a glycol component. For example, 1,3-propanediol can bepart of or the sole glycol component of personal care and cosmeticcompositions.

It is contemplated herein that other renewably-based orbiologically-derived glycols, such as ethylene glycol, dietheyleneglycol, triethylene glycol, 1,2 propylene glycol, dipropylene glycol,tripropylene glycol, neopentyl glycol and bisphenol A, among others, canbe used in the biodegradable compositions of the present invention.

Bio-PDO can be combined with one or more of any ingredients typicallyused in biodegradable compositions. Set forth below are typicalbiodegradable end use products as well as typical ingredients usedtherein, general formulations and examples, all of which can be used inthe invention.

Personal Care and Cosmetics

While in it is a general practice in the art to distinguish betweenpersonal care compositions and cosmetic compositions, indeed it is oftenthe case certain personal care products will often be referred to ascosmetic products, and vice versa. As such, in order to simplify andavoid confusion, it is intended, for purposes of this application, thatthe words “personal care” and “cosmetics”, while used separately attimes, will be considered synonymous and will be used interchangeablythroughout the application to describe the compositions of thisinvention.

In compositions of the invention that are generally referred to in theart as cosmetic compositions (also referred to in the art as endermicliminent compositions), Bio-PDO can serve as a humectant, solvent,neutralizer, preservative, emulsifier, emollient, softening agent,handfeel effector, water activity reducer and/or fragrance enhancer.Similarly, in compositions of the invention that are generally referredto in the art as personal care compositions, the Bio-PDO typicallyserves as a surfactant, humectant, solvent, neutralizer, emulsifier,preservative and/or fragrance enhancer.

Some examples of typical personal care and cosmetic compositionsinclude, but are not limited to, lipstick, lip gloss, lip pencil, eyeshadows, foundation, blush, liquid rouge, facial powder, make-up,concealer, gel eye color, mascara, lip gloss, eye pencil, lip pencil,eye make-up remover, eye liners, eye shadow, lotion eye color, gel eyecolor, nail polish, lipstick nail polish, gel polish removers, liquidrouges, blush, and facial powder, skin care composition, skin cleansingcomposition, skin cleansing bar, skin cleansing liquid, facial lotion,facial cream, cream moisturizer, body wash, body lotion; foot careproducts like foot cream, hand cream; deodorant and antiperspirantsticks, roll-ons, aerosols, gels, creams, pump sprays, powders,odor-masking, odor-neutralizing, odor-quenching, odor-inhibiting;cologne sticks, perfumes, shaving cream, shaving lotion, creamdepilatory, lotion depilatory, wax depilatory, facial mask made withclay materials, anti-aging product, anti-wrinkle product, anti-celluliteproduct, cuticle remover, cuticle cream, acne cream, acne cleansingscrub; oral products like toothpaste, gargle, mouth wash, mouth rinse,film, gum; shampoo, hair care products like conditioner, hair treatmentcream, styling gel, styling foam, hair mousse, hair spray, set lotion,blow-styling lotion, hair color lotion, creams and dyes, hair bleachingcream, hair relaxer, hair straightener, curl activator gel, fragranthair gloss, dressings (styling products & aids); bleach; sun careproducts like sun stick and sun screen, artificial tanning products,skin-whitening products; soaps, hand wash, body scrub, hand scrub,bubble bath, bath oils, instant hand sanitizer, hand sanitizer gels,antibacterial hand cleaner, deodorants, anti-perspirants, baby lotion,diaper rash cream, wet wipe, and baby bath, and vitamin creams, amongothers. This list is not intended to be all-inclusive or otherwiselimiting in any way, and those having skill in the art are very familiarwith all types of personal care and cosmetic products that can functioneffectively with the Bio-PDO glycol component of the invention.

Bio-PDO can be present in the aforementioned personal care and cosmeticscompositions in amounts well known to those of ordinary skill in theappropriate art, typically up to about 12% by weight based on the weightof the total composition, though some compositions, for example, bathpreparations may contain as much as 50% glycol, and some specialtyformulations like vitamin creams can contain even higher percentages ofglycol up to as much as 65%, and deodorants up to as much as 85%.

Preferred Bio-PDO Concentration Ranges

Baby products, such as, for example, baby shampoos, soaps, wipes,lotions, oils, powders, and creams, wherein preferred Bio-PDOconcentration ranges are from about 0.1% to about 25% by weight, andmore preferably from about 1% to about 10% by weight, and even morepreferably 1 to 5%.

Bath preparations such as, for example, bath oils, tablets, and salts;bubble baths and bath capsules, wherein preferred Bio-PDO concentrationranges are from about 0.001% to about 50%, and more preferably fromabout 0.1% to about 10%, and even more preferably from about 1% to about5%.

Eye makeup preparations such as, for example, eyebrow pencil; eyeliner;eye shadow; eye lotion; eye makeup remover; and mascara, whereinpreferred Bio-PDO concentration ranges are from about 0.001% to about75%, more preferably 0.01% to about 25%, and even more preferably, 0.05%to about 5%.

Fragrance preparations such as, for example, colognes and toilet waters;perfumes; powders (dusting and talcum) (excluding aftershave talc); andsachets, wherein preferred Bio-PDO concentration ranges are from about0.001% to about 99%, more preferably from about 0.01% to about 10%, andeven more preferably from about 0.05% to about 5%.

Hair preparations (noncoloring) such as, for example, hair conditioners;hair sprays (aerosol fixatives); hair straighteners; permanent waves;rinses (noncoloring); shampoos (noncoloring); tonics, dressings, andother hair grooming aids; and wave sets, wherein preferred Bio-PDOconcentration ranges are from about 0.001% to about 90%, more preferablyfrom about 0.01% to about 50%, and even more preferably from about 0.05%to about 10%.

Hair coloring preparations such as, for example, hair dyes and colors(requiring caution statement & patch test); hair tints; hair rinses(coloring); hair shampoos (coloring); hair color sprays (aerosol); hairlighteners with color; and hair bleaches, wherein preferred Bio-PDOconcentration ranges are from about 0.001% to about 50%, more preferablyfrom about 0.1% to about 25%, and even more preferably, from about 1% toabout 10%.

Makeup preparations (not eye) such as, for example, blushers (alltypes); face powders; foundations; leg and body paints; lipstick; makeupbases; rouges; and makeup fixatives, wherein preferred Bio-PDOconcentration ranges are from about 0.001% to about 99%, more preferablyfrom about 0.01% to about 25%, and even more preferably from about 0.05%to about 10%.

Manicuring preparations such as, for example, basecoats and undercoats;cuticle softeners; nail creams and lotions; nail extenders; nail polishand enamel; and Nail polish and enamel removers, wherein preferredBio-PDO concentration ranges are from about 0.001% to about 50%, morepreferably from about 0.1% to about 10%, and even more preferably fromabout 1% to about 5%.

Oral hygiene products such as, for example, dentifrices (aerosol,liquid, pastes, and powders); and mouthwashes and breath fresheners(liquids and sprays), wherein preferred Bio-PDO concentration ranges arefrom about 0.001% to about 80%, and more preferably from about 1% toabout 5%.

Personal cleanliness products, such as, for example, bath soaps anddetergents; deodorants (underarm); antiperspirants; douches; andfeminine hygiene deodorants, wherein preferred Bio-PDO concentrationranges are from about 0.001% to about 99%, more preferably from about0.01% to about 50%, and even more preferably from about 0.05% to about10%.

Shaving preparations such as, for example, shaving lotions, aftershavelotions; beard softeners; men's talcum; preshave lotions (all types);shaving cream (aerosol, brushless, and lather); and shaving soap (cakes,sticks, etc.), wherein preferred Bio-PDO concentration ranges are fromabout 0.001% to about 50%, more preferably from about 0.01% to about10%, and even more preferably from about 0.1% to about 5%.

Skin care preparations (creams, lotions, powder, and sprays), such as,for example, cleansing (cold creams, cleansing lotions, liquids, andpads); depilatories; face and neck (excluding shaving preparations);body and hand (excluding shaving preparations); foot powders and sprays;hormone products; moisturizing; night; paste masks (mud packs); skinlighteners; skin fresheners; and wrinkle-smoothing products (removers),wherein preferred Bio-PDO concentration ranges are from about 0.001% toabout 50%, more preferably from about 0.01% to about 15%, and even morepreferably from about 0.05% to about 5%.

Suntan preparations such as, for example, suntan gels, creams, liquids,powders, sticks and sprays; and indoor tanning preparations; whereinpreferred Bio-PDO concentration ranges are from about 0.001% to about25%, and more preferably from about 1% to about 10%.

Preservatives (antiseptic/antifungal/antimicrobial agents), such as, forexample, parabens; salicylic acid; sorbic acid; and phenoxy elthanol,wherein preferred Bio-PDO concentration ranges are from about 0.001% toabout 100%, and more preferably from about 95% to about 99.99%.

Typical Broad Formulations for Certain End Use Applications

Set forth in this section are general, broad range formulations for ahandful of personal care and cosmetic end use applications intended toprovide the reader with a general idea of the variety of applicationsand uses for Bio-PDO in personal care and cosmetic products. Thissection is by no means intended to be limiting in any way, and thosehaving skill in the art can readily determine appropriate uses ofBio-PDO as a glycol component in all other known personal care andcosmetic products.

Skin Products

Some examples of vehicles for skin product formulations includeoil-in-water emulsion (O/W), water-in-oil emulsion (W/O),water-in-silicon (W/Si), Oleaginous emulsion, water-soluble emulsion,aqueous gel emulsion and absorption bases emulsion.

A typical O/W skin product formulation may include 5%-35% surfactant,2%-15% emulsifier, 0.5%-15% Bio-PDO and 5%-60% water.

A typical W/O skin product formulation may include 45%-80% surfactant,0.5%-5% emulsifier, 0.5%-15% Bio-PDO and 20%-50% water.

A typical O/W/O & W/O/W skin product formulation may include 18%-23%surfactant, 3%-8% emulsifier, 0.5%-15% Bio-PDO and 60%-70% water.

A typical W/Si & O/Si skin product formulation may include 5-35%surfactant, 2%-3% emulsifier, 0.5%-15% Bio-PDO; and 60%-80% water.

Hair Products

Some examples of vehicles for hair product formulations includeoil-in-water emulsion (O/W), water-in-oil emulsion (W/O),Water-in-silicon (W/Si), oleaginous, water-soluble, aqueous gel, andabsorption bases, among others.

A typical shampoo & conditioner may include 0.1-40% surfactant; 0.1-10%Bio-PDO, and 35-55% water.

A typical liquid & cream color dye may include 70-80% dye base, 5-25%Bio-PDO, 0.1-5% dye intermediates, and 0.1-10% developer

A typical relaxer or straightener formulation may include 30-60%oil/wax, 10-60% water, 1-10% Bio-PDO, and 0.1-5.0% caustic.

A typical dressing formulation may include 0.01-7% filmformer/plasticizer, 0.01-90% Bio-PDO, 0-30% propellant and 10-90% water.

Oral Products

Some examples of vehicles for oral product formulations include solidforms, such as paste, gel, cream, and ointment; and liquid forms such aswashes, rinses, gargles, and sprays.

A typical tooth paste/gel/cream/ointment formulation may include1-60/15-55/30-50% abrasive, 1-80/1-50/1-30% Bio-PDO;0.01-30/0.1-15/0.5-5% thickener, 0.01-10/0.1-7.5/0.5-5% surfactant, and0.0001-2/0.001-1/0.01-0.5% antiseptic.

A typical mouth wash/rinse/gargle/spray may include 0.1-55/0.5-40/1-25%Bio-PDO, 0.1-55/0.5-40/1-25% alcohol, 0.01-10/0.1-7.5/0.5-5% thickener,0.001-2/0.01-1/0.1-0.5% surfactant, and 0.0001-5/0.001-2.5/0.01-1%antiseptic.

Color Cosmetics

Some examples of vehicles for color cosmetic formulations include, forfoundation: O/W & W/O emulsions, anhydrous powders & sticks, and oil &aqueous suspensions; for mascara: O/W & W/O emulsions and anhydroussolvent; for eyeliner: aqueous and anhydrous; for eye shadow: creams andpowders; for blushers: powders; and for lip Color: gloss & matte(classical) and solvent (Volatile).

A typical formulation for an O/W foundation product may include 2%-15%emulsifier, 50%-75% Bio-PDO, 6%-12% pigment and 8%-12% pearlizer

A typical formulation for a W/O foundation product may include 4%-6%emulsifier, 50%-75% Bio-PDO, 6%-12% pigment and 8%-12% pearlizer.

A typical formulation for an anhydrous foundation product may include30-60% Bio-PDO, 5-10% wax, 0.5-1.0% wetting agents, and 30-60%texturizing agent.

A typical formulation for a O/W, W/O mascara product may include 4%-10%emulsifier, 2%-5% thickener, 40%-60% Bio-PDO and 6%-12% pigment.

A typical formulation for a solvent-based mascara product may include40-60% Bio-PDO 10-20% wax, 3-10% resin, 3-7% thickener, 5-15% colorant,and 2-10% filler.

A typical formulation for an eye shadow product may include 35-55%Bio-PDO, 1.5-3.5% thickener, 7-12% wax, 3-8% emollient, 5-20% colorant,and 5-20% filler.

A typical formulation for an eye liner product may include 50-70% water,0.5-1.5% thickener, 4-12% Bio-PDO, 10-20% colorant, 5-10% alcohol, and3-8% dispersant.

A typical formulation for a classical lipstick product may include40-70% Bio-PDO, 8-15% wax, 2-5% plasticizer, 0.5-8% colorant, 1-6%pearlizer, 1-15% filler and 0.1-0.5% preservative.

A typical formulation for a volatile lipstick product may include 25-60%solvent, 1-85% Bio-PDO, 10-25% wax, 1-10% fixative, 1-15% filler and1-15% colorant.

Deodorants

Some examples of vehicles for deodorant formulations include sticks,aerosols and pump sprays, among others well known in the art.

A typical formulation for a stick deodorant may include 5-9% emulsifier,1-30% Bio-PDO, 5-80% clarifying agent, and 0.1-2% deodorizer.

A typical formulation for an aerosol deodorant may include 0.1-2%emulsifier, 30-50% Bio-PDO, 5-80% clarifying agent, 0.1-2% deodorizer,and 40-60% propellant

A typical formulation for a hydroalcoholic pump spray deodorant mayinclude 30-40% solvent, 50-70% Bio-PDO, 0.1-5% solubilizer, and 0.1-5%deodorizer.

A typical formulation for a Phase Inversion Temperature Emulsion (PIT)emulsion pump spray deodorant may include 0.1-10% surfactant, 0.1-15%oil, 65-85% Bio-PDO, and 0.1-5% deodorizer.

Antiperspirants

Some examples of vehicles for antiperspirant formulations include sticks(suspension, gel, and emulsion), roll-ons (Emulsion O/W, W/O, W/Si,Clear Hydroalcoholic and suspension), and aerosols, among others wellknown in the art.

A typical stick antiperspirant formulation may include 1-30% gel agent,15-55% Bio-PDO, 1-20% emollient, 0-20% surfactant, and 15-55%antiperspirant.

A typical roll-on antiperspirant formulation may include 0-5%surfactant, 0.5-15% gel agent, 0-5% emollient, 15-25% antiperspirant and60-85% Bio-PDO.

A typical aerosol antiperspirant formulation may include 0.1-2% gelagent, 5-15% antiperspirant, 5-20% Bio-PDO, and 70-80% propellant.

Ingredient Listings:

Cosmetic and personal care compositions of the invention preferablycontain Bio-PDO and one or more conventional cosmetic or dermatologicaladditives or adjuvants including, but not limited to, carriers; actives;fillers; surfactants; thixotropic agents; antioxidants; preservingagents; dyes; pigments; fragrances; thickeners; vitamins; hormones;moisturizers; UV absorbing sunscreens; UV scattering inorganicsunscreens; wetting agents; cationic, anionic, nonionic, or amphotericpolymers; and hair coloring active substances.

Conventional optional ingredients are well known to those skilled in theart. These include, but are not limited to, emollients, oil absorbents,antimicrobial agents, binders, buffering agents, denaturants, cosmeticastringents, external analgesics, film formers, humectants, opacifyingagents, perfumes, pigments, skin soothing and healing agents,preservatives, propellants, skin penetration enhancers, solvents,suspending agents, emulsifiers, cleansing agents, thickening agents,solubilizing agents, waxes, inorganic and organic sunblocks, sunlesstanning agents, antioxidants and/or radical scavengers, chelatingagents, anti-acne agents, anti-inflammatory agents, desquamationagents/exfoliants, organic hydroxy acids, vitamins, natural extracts andinorganic particulates such as silica and boron nitride. Nonexclusiveexamples of such materials are described in Harry's Cosmeticology, 7thEd., Harry & Wilkinson (Hill Publishers, London 1982); in PharmaceuticalDosage Forms—Disperse Systems; Lieberman, Rieger & Banker, Vols. 1(1988) & 2 (1989); Marcel Decker, Inc.; in The Chemistry and Manufactureof Cosmetics, 2nd. Ed., deNavarre (Van Nostrand 1962-1965); and in TheHandbook of Cosmetic Science and Technology, 1st Ed. Knowlton & Pearce(Elsevier 1993) can also be used in the present invention.

However, it is to be understood that the active and other ingredientsuseful herein can in some instances provide more than one cosmeticand/or therapeutic benefit or operate via more than one mode of action.Such components are particularly preferred additional ingredients, theiruse often saving both money and formulation space. Examples of suchcomponents include ethanol, isopropyl myristate, and the many componentsthat can act as both structurants and sensory modifiers, for examplesilica. Therefore, classifications herein are made for the sake ofconvenience and are not intended to limit an ingredient to theparticularly stated application or applications listed.

The adjuvants are well known in the field of cosmetics and are describedin many publications, for example see Harry's Cosmeticology, 8^(th)Edition, Martin Rieger, ed. Chemical Publishing, New York (2000).Amounts of adjuvants generally present in the aforementioned cosmeticand personal care compositions are well known in the art (see, e.g.,co-owned, co-filed U.S. patent application entitled “Personal CareCompositions”, Attorney Docket No. CL3428 US PRV

Carriers

The compositions of the present invention preferably comprise a safe andeffective amount of an acceptable carrier, suitable for topicalapplication to the skin within which the essential materials andoptional other materials are incorporated to enable the essentialmaterials and optional components to be delivered to the skin at anappropriate concentration. The carrier can thus act as a diluent,dispersant, solvent, or the like for any active ingredients whichensures that they can be applied to, and distributed evenly over, theselected target at an appropriate concentration.

The type of carrier utilized in the present invention depends on thetypes of product form desired for the composition. The topicalcompositions useful in the subject invention may be made into a widevariety of product forms such as are known in the art. These include butare not limited to lotions, creams, gels, sticks, sprays, ointments,pastes and mousses. These product forms may comprise several types ofcarriers including, but not limited to, solutions, aerosols, emulsions,gels, solids and liposomes.

It is preferred that the carrier(s) of the invention contain adermatologically acceptable, hydrophilic diluent, such as, preferably,renewably-based, biodegradable 1,3-propanediol.

Actives Actives for Regulating Skin Condition

The compositions of the invention optionally comprise a safe andeffective amount of an active for regulating skin condition includingprophylactically and therapeutically regulating the skin condition.Prophylactically regulating skin condition includes delaying,minimizing, and/or preventing visible and/or tactile discontinuities inthe skin. Therapeutically regulating the skin condiments includesameliorating e.g., diminishing, minimising, and/or effacing suchdiscontinuities. Regulating the skin condition also involves improvingthe skin appearance and/or feel. Also included is regulating the signsof ageing which can involve prophylactically regulating and/ortherapeutically regulating one or more of such signs e.g., fine lines,wrinkles, pores etc.

Ingredients that are known to be useful for regulating the skincondition are selected from Vitamin B3 compounds, retinoids, andcombinations thereof. As described for the humectants, theaforementioned compounds may, when used by themselves, give rise to ahigh level of tack, especially when used at the higher levels. It hasbeen found, however, that this tacky feel can be offset by using theparticulates of the present invention. The compositions of the presentinvention preferably comprise from about 0.1% to about 15%, morepreferably from about 0.3% to about 10%, even more preferably from about1 to about 5% of the active.

As used herein, “vitamin B3 compound” means a compound having theformula: 1

wherein R is —CONH₂ (i.e., niacinamide), —COOH (i.e., nicotinic acid) or—CH₂OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of anyof the foregoing. One or more vitamin B₃ compounds, or their salts, ormixtures thereof may be used herein. In a preferred embodiment, thevitamin B₃ compound typically contains less than about 50% of thecompound in a salt form. As used herein, “retinoid” includes all naturaland/or synthetic analogues of Vitamin A or retinol-like compounds whichpossess the biological activity of Vitamin A in the skin as well as thegeometric isomers and stereoisomers of these compounds. Again, all skinregulating materials discussed in application WO 00/24372 should beconsidered as suitable for use in the present invention.

Anti-Bacterial Actives

Any antibacterial active acceptable for underarm application can be usedin the deodorant compositions. Antibacterial ingredients, bynon-limiting example, include those selected from the group consistingof triclosan, bacteriostatic quaternary ammonium compounds such asbenzalkonium chloride, benzethonium chloride, cetyl pyridium chloride,lauryl pyridium chloride and methyl benzethonium chloride; triclocarbon;zinc phenol sulfonate; zinc ricinoleate; triethyl citrate; essentialoils; and combinations thereof and the like. The most preferreddeodorant active is triclosan. The fragrance may also have antibacterialproperties.

Anti-Inflammatory Agents

A safe and effective amount of an anti-inflammatory agent may be addedto the compositions of the subject invention, preferably from about 0.1%to about 5%, more preferably from about 0.1% to about 2%, of thecomposition. The anti-inflammatory agent enhances the skin appearancebenefits of the present invention, e.g., such agents contribute to amore uniform and acceptable skin tone or colour. The exact amount ofanti-inflammatory agent to be used in the compositions will depend onthe particular anti-inflammatory agent utilised since such agents varywidely in potency. Anti-inflammatory agents useful herein includesteroids such as hydrocortisone; non-steroidal anti-inflammatory drugs(NSAIDS) such as ibuprofen; panthenol and ether and ester derivativesthereof e.g. panthenol ethyl ether, panthenyl triacetate; pantothenicacid and salt and ester derivatives thereof, especially calciumpantothenate; aloe vera, bisabolol, allantoin and compounds of theliquorice (the plant genus/species Glycyrrhiza glabra) family, includingglycyrrhetic acid, glycyrrhizic acid, and derivatives thereof e.g. saltssuch as ammonium glycyrrhizinate and esters such as stearylglycyrrhetinate. Particularly preferred herein are panthenol,pantothenic acid and their ether, ester or salt derivatives and mixturesthereof; suitable levels are from about 0.1 to about 5%, preferably fromabout 0.5 to about 3%. Panthenol is especially preferred.

Antimicrobial Agents

Conventional organic anti-microbial agents may also be advantageouslyemployed in the methods and products of the present invention. Levels ofincorporation are preferably from 0.01% to 3%, more preferably from0.03% to 0.5% by weight of the composition in which they are present,excluding any volatile propellant also present. Most of the classes ofagents commonly used in the art can be utilised. Preferred additionalorganic anti-microbials are bactericides, for example quaternaryammonium compounds, like cetyltrimethylammonium salts; chlorhexidine andsalts thereof; and diglycerol monocaprate, diglycerol monolaurate,glycerol monolaurate, and similar materials, as described in “DeodorantIngredients”, S. A. Makin and M. R. Lowry, in “Antiperspirants andDeodorants”, Ed. K. Laden (1999, Marcel Dekker, New York). Morepreferred additional anti-microbials for use in the compositions of theinvention are polyhexamethylene biguanide salts;2,4,4′-trichloro,2′-hydroxy-diphen-yl ether (triclosan); and3,7,11-trimethyldodeca-2,6,10-trienol (farnesol).

Inorganic anti-microbial agents may also be used in the compositions ofthe invention. Such materials can often function as anti-perspirantactives when present at a suitable concentration. Examples are oftenselected from astringent active salts, including, in particular,aluminium, zirconium and mixed aluminium/zirconium salts, including bothinorganic salts, salts with organic anions and complexes. Preferredastringent salts include aluminium, zirconium and aluminium/zirconiumhalides and halohydrate salts, such as chlorohydrates. When included,preferred levels of incorporation are from 0.5% to 60%, particularlyfrom 5% to 30% or 40% and especially from 5% or 10% to 30% or 35% byweight of a composition. Especially preferred aluminium halohydratesalts, known as activated aluminium chlorohydrates, are described in EP6,739 (Unilever PLC and NV). Zirconium aluminium chlorohydrate activesare also preferred materials, as are the so-called ZAG(zirconium-aluminium-glycine) complexes, for example those disclosed inU.S. Pat. No. 3,792,068 (Procter and Gamble Co.). Zinc phenol sulphonatemay also be used, preferably at up to 3% by weight of the composition.

Anti-Oxidants/Radical Scavengers

Compositions of the subject invention can further include ananti-oxidant/radical scavenger. The anti-oxidant/radical scavenger isespecially useful for providing protection against UV radiation whichcan cause increased scaling or texture changes in the stratum corneumand against other environmental agents which can cause skin damage.Suitable amounts are from about 0.1% to about 10%, more preferably fromabout 1% to about 5%, of the composition.

Anti-oxidants/radical scavengers such as ascorbic acid (vitamin C) andits salts, ascorbyl esters of fatty acids, ascorbic acid derivatives(e.g., magnesium ascorbyl phosphate), .beta.-carotene, tocopherol(vitamin E), tocopherol sorbate, tocopherol acetate, other esters oftocopherol, butylated hydroxy benzoic acids and their salts, gallic acidand its alkyl esters, especially propyl gallate, uric acid and its saltsand alkyl esters, sorbic acid and its salts, amines (e.g.,N,N-diethylhydroxylamine, amino-guanidine), sulfhydryl compounds (e.g.,glutathione), dihydroxy fumaric acid and its salts, bioflavonoids,lysine, methionine, proline, superoxide dismutase, silymarin, teaextracts, grape skin/seed extracts, melanin, and rosemary extracts maybe used. Preferred anti-oxidants/radical scavengers are selected fromtocopherol acetate, tocopherol sorbate and other esters of tocopherol,more preferably tocopherol acetate. As described for the humectants, theaforementioned compounds may, when used by themselves, give rise to ahigh level of tack, especially when used at the higher levels. It hasbeen found, however, that this tacky feel can be offset by using theparticulates of the present invention.

Chelators

The inclusion of a chelating agent is especially useful for providingprotection against UV radiation which can contribute to excessivescaling or skin texture changes and against other environmental agentswhich can cause skin damage. A suitable amount is from about 0.01% toabout 1%, more preferably from about 0.05% to about 0.5%, of thecomposition. Exemplary chelators that are useful herein are disclosed inU.S. Pat. No. 5,487,884, incorporated herein by reference. Preferredchelators useful in compositions of the subject invention areethylenediamine tetraacetic acid (EDTA), furildioxime, and derivativesthereof.

Colorants and Preservatives

Further additional components that may also be included are colorantsand preservatives, for example C1-C3 alkyl parabens.

Desquamation Agents/Exfoliants

A safe and effective amount of a desquamation agent may be added to thecompositions of the subject invention, more preferably from about 0.1%to about 10%, even more preferably from about 0.2% to about 5%, alsopreferably from about 0.5% to about 4% of the composition. Desquamationagents enhance the skin appearance benefits of the present invention.For example, the desquamation agents tend to improve the texture of theskin (e.g., smoothness). A variety of desquamation agents are known inthe art and are suitable for use herein, including organic hydroxy acidssuch as salicylic acid, glycolic acid, lactic acid, 5-octanoyl salicylicacid, hydroxyoctanoic acid, hydroxycaprylic acid, and lanolin fattyacids. One desquamation system that is suitable for use herein comprisessulphydryl compounds and zwitterionic surfactants and is described in WO96/01101, incorporated herein by reference. Another desquamation systemthat is suitable for use herein comprises salicylic acid andzwitterionic surfactants and is described in WO 95/13048, incorporatedherein by reference. Salicylic acid is preferred.

Emollients

Emollients are a known class of materials in this art, imparting asoothing effect to the skin. These are ingredients which help tomaintain the soft, smooth, and pliable appearance of the skin.Emollients are also known to reduce whitening on the skin and/or improveaesthetics. Examples of chemical classes from which suitable emollientscan be found include:

(a) fats and oils which are the glyceryl esters of fatty acids, ortriglycerides, normally found in animal and plant tissues, includingthose which have been hydrogenated to reduce or eliminate unsaturation.Also included are synthetically prepared esters of glycerin and fattyacids. Isolated and purified fatty acids can be esterified with glycerinto yield mono-, di-, and triglycerides. These are relatively pure fatswhich differ only slightly from the fats and oils found in nature. Thegeneral structure may be represented by Formula III:

wherein each of R₁, R₂, and R₃ may be the same or different and have acarbon chain length (saturated or unsaturated) of 7 to 30. Specificexamples include peanut oil, sesame oil, avocado oil, coconut, cocoabutter, almond oil, safflower oil, corn oil, cotton seed oil, castoroil, hydrogenated castor oil, olive oil, jojoba oil, cod liver oil, palmoil, soybean oil, wheat germ oil, linseed oil, and sunflower seed oil;

(b) hydrocarbons which are a group of compounds containing only carbonand hydrogen. These are derived from petrochemicals. Their structurescan vary widely and include aliphatic, alicyclic and aromatic compounds.Specific examples include paraffin, petrolatum, hydrogenatedpolyisobutene, and mineral oil.

(c) esters which chemically, are the covalent compounds formed betweenacids and alcohols. Esters can be formed from organic carboxylic acidsand any alcohol. Esters here are derived from monocarboxylic acids andalcohols (mono alcohols or polyols as glycols). The general structurewould be R₄COOR₅. The chain length for R₄ and R₅ can vary from 7 to 30and can be saturated or unsaturated, straight chained or branched.Specific examples include isopropyl myristate, isopropyl palmitate,isopropyl stearate, isopropyl isostearate, butyl stearate, octylstearate, hexyl laurate, cetyl stearate, diisopropyl adipate, isodecyloleate, diisopropyl sebacate, isostearyl lactate, C₁₂₋₁₅ alkylbenzoates, myreth-3 myristate, dioctyl malate, neopentyl-glycoldiheptanoate, neopentyl glycol dioctanoate, dipropylene glycoldibenzoate, C₁₂₋₁₅ alcohols lactate, isohexyl decanoate, isohexylcaprate, diethylene glycol dioctanoate, octyl isononanoate, isodecyloctanoate, diethylene glycol diisononanoate, isononyl isononanoate,isostearyl isostearate, behenyl behenate, C₁₂₋₁₅ alkyl fumarate,laureth-2 benzoate, propylene glycol isoceteth-3 acetate, propyleneglycol ceteth-3 acetate, octyldodecyl myristate, cetyl ricinoleate,myristyl-myristate.

Esters, made using compounds such as Bio-PDO or other biologicallyderived glycols, can also be used in these compositions. The estersproduced include all the appropriate conjugate mono and diesters ofbiologically derived 1,3 propanediol using organic carboxylic acids.Some esters in particular that are produced include propanedioldistearate and monostearate, propandiol dilaurate and monolaurate,propanediol dioleate and monooleate, propanediol divalerate andmonovalerate, propanediol dicaprylate and monocaprylate, propanedioldimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

(d) saturated and unsaturated fatty acids which are the carboxylic acidsobtained by hydrolysis of animal or vegetable fats and oils. These havegeneral structure R₆COOH with the R₆ group having a carbon chain lengthbetween 7 and 30, straight chain or branched. Specific examples includelauric, myristic, palmitic, stearic, oleic, linoleic and behenic acid.

(e) saturated and unsaturated fatty alcohols (including guerbetalcohols) with general structure R₇OH where R₇ can be straight orbranched and have carbon length of 7 to 30. Specific examples includelauryl, myristyl, cetyl, isocetyl, stearyl, isostearyl, oleyl,ricinoleyl and erucyl alcohol;

(f) lanolin and its derivatives which are a complex esterified mixtureof high molecular weight esters of (hydroxylated) fatty acids withaliphatic and alicyclic alcohols and sterols. General structures wouldinclude R₉CH₂—(OCH₂CH₂)_(noH) where R⁸ represents the fatty groupsderived from lanolin and n=5 to 75 or R9CO—(OCH₂CH₂)_(n)OH where R₉CO—represents the fatty acids derived from lanolin and n=5 to 100. Specificexamples include lanolin, lanolin oil, lanolin wax, lanolin alcohols,lanolin fatty acids, isopropyl lanolate, ethoxylated lanolin andacetylated lanolin alcohols.

(g) alkoxylated alcohols wherein the alcohol portion is selected fromaliphatic alcohols having 2-18 and more particularly 4-18 carbons, andthe alkylene portion is selected from the group consisting of ethyleneoxide, and propylene oxide having a number of alkylene oxide units from2-53 and, more particularly, from 2-15. Specific examples include PPG-14butyl ether and PPG-53 butyl ether.

(h) silicones and silanes the linear organo-substituted polysiloxaneswhich are polymers of silicon/oxygen with general structure:

(1) (R₁₀)₃SiO(Si(R₁₁)₂₀)_(x)Si (R₁₂)₋₃ where R₁₀, R₁₁ and R₁₂ can be thesame or different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl;

(2) HO(R₁₄)₂SiO(Si(R₁₅)₂₀)_(x)Si (R₁₆)₂OH, where R₁₄, R₁₅ and R₁₆ can bethe same or different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl; or

(3) organo substituted silicon compounds of formula R₁₇Si(R₁₈)₂OSiR₁₉₃which are not polymeric where R₁₇, R₁₈ and R₁₉ can be the same ordifferent and are each independently selected from the group consistingof phenyl and C1-C60 alkyl optionally with one or both of the terminal Rgroups also containing an hydroxyl group. Specific examples includedimethicone, dimethiconol behenate, C30-45 alkyl methicone,stearoxytrimethylsilane, phenyl trimethicone and stearyl dimethicone.

(i) mixtures and blends of two or more of the foregoing.

Emollients of special interest include C12-15 alkyl benzoate (FINSOLV TNfrom Finetex Inc., Elmwood Park, N.J.), isopropyl myristate; andneopentyl glycol diheptanoate.

The emollient or emollient mixture or blend thereof incorporated incompositions according to the present invention can, illustratively, beincluded in amounts of 0.1-20%, preferably 1-15%, more preferably 1-10%,by weight, of the total weight of the composition.

Emulsifiers/Surfactants

Compositions herein preferably contain an emulsifier and/or surfactant,generally to help disperse and suspend the discontinuous phase withinthe continuous aqueous phase. A surfactant may also be useful if theproduct is intended for skin cleansing. For convenience hereinafteremulsifiers will be referred to under the term ‘surfactants’, thus‘surfactant(s)’ will be used to refer to surface active agents whetherused as emulsifiers or for other surfactant purposes such as skincleansing. Known or conventional surfactants can be used in thecomposition, provided that the selected agent is chemically andphysically compatible with essential components of the composition, andprovides the desired characteristics. Suitable surfactants includenon-silicone derived materials, and mixtures thereof. All surfactantsdiscussed in application WO 00/24372 should be considered as suitablefor use in the present invention.

The compositions of the present invention preferably comprise from about0.05% to about 15% of a surfactant or mixture of surfactants. The exactsurfactant or surfactant mixture chosen will depend upon the pH of thecomposition and the other components present.

Preferred surfactants are nonionic. Among the nonionic surfactants thatare useful herein are those that can be broadly defined as condensationproducts of long chain alcohols, e.g. C8-30 alcohols, with sugar orstarch polymers i.e., glycosides. Other useful nonionic surfactantsinclude the condensation products of alkylene oxides with fatty acids(i.e. alkylene oxide esters of fatty acids). These materials have thegeneral formula RCO(X)nOH wherein R is a C10-30 alkyl group, X is—OCH2CH2- (i.e. derived from ethylene glycol or oxide) or —OCH2CHCH3-(i.e. derived from propylene glycol or oxide), and n is an integer fromabout 6 to about 200. Other nonionic surfactants are the condensationproducts of alkylene oxides with 2 moles of fatty acids (i.e. alkyleneoxide diesters of fatty acids). These materials have the general formulaRCO(X)nOOCR wherein R is a C10-30 alkyl group, X is —OCH2CH2- (i.e.derived from ethylene glycol or oxide) or —OCH2CHCH3- (i.e. derived frompropylene glycol or oxide), and n is an integer from about 6 to about100. Even further suitable examples include a mixture of cetearylalcohols, cetearyl glucosides such as those available under the tradename Montanov 68 from Seppic and Emulgade PL68/50 from Cognis UK Ltd. Anexample of a suitable cetearyl glucoside material without added fattyalcohols is Tego® Care CG90 commercially available from GoldschmidtGmbH. Other nonionic surfactants are fatty alkanolamides with thegeneral formula R—CO—N—(CH2CH20H)n where R is a hydrocarbon chain and nis the integer 1 or 2. The most commonly used are cocoamide DEA(diethanolamide) and cocoamide MEA (monoethanolamide).

The hydrophilic surfactants useful herein can alternatively oradditionally include any of a wide variety of cationic, anionic,zwitterionic, and amphoteric surfactants such as are known in the art.See, e.g., McCutcheon's, Detergents and Emulsifiers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Pat.No. 5,011,681 to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No.4,421,769 to Dixon et al., issued Dec. 20, 1983; and U.S. Pat. No.3,755,560 to Dickert et al., issued Aug. 28, 1973. A wide variety ofanionic surfactants are also useful herein. See, e.g., U.S. Pat. No.3,929,678, to Laughlin et al., issued Dec. 30, 1975.

A wide variety of anionic surfactants are also useful herein. See, e.g.,U.S. Pat. No. 3,929,678, to Laughlin et al., issued Dec. 30, 1975.Exemplary anionic surfactants include the alkoyl isethionates (e.g.,C.12-C30), alkyl and alkyl ether sulfates and salts thereof, alkyl andalkyl ether phosphates and salts thereof, alkyl methyl taurates (e.g.,C12-C30), and soaps (e.g., alkali metal salts, e.g., sodium or potassiumsalts) of fatty acids.

Amphoteric and zwitterionic surfactants are also useful herein. Examplesof amphoteric and zwitterionic surfactants which can be used in thecompositions of the present invention are those which are broadlydescribed as derivatives of aliphatic secondary and tertiary amines inwhich the aliphatic radical can be straight or branched chain andwherein one of the aliphatic substituents contains from about 8 to about22 carbon atoms (preferably C8-C18) and one contains an anionic watersolubilising group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate. Examples are alkyl imino acetates, and iminodialkanoatesand aminoalkanoates, imidazolinium and ammonium derivatives. Othersuitable amphoteric and zwitterionic surfactants are those selected fromthe group consisting of betaines, sultaines, hydroxysultaines, andbranched and unbranched alkanoyl sarcosinates, and mixtures thereof.

Fragrance

Fragrance is also a desirable additional component in the compositionsof the invention. Suitable materials include conventional perfumes, suchas perfume oils and also include so-called deo-perfumes, as described inEP 545,556 and other publications. These latter materials may alsoqualify as additional organic anti-microbial agents. Levels ofincorporation are preferably up to 4% by weight, particularly from 0.1%to 2% by weight, and especially from 0.7% to 1.7% by weight of acomposition. Synergies can exist between the essential components of theinvention and certain fragrance components—long-lasting odor controlbeing the result.

The fragrance may be selected from the group consisting of anycosmetically acceptable fragrance or fragrances acceptable for topicalapplication. The fragrance should be suitable for masking malodor, suchas malodor associated with human sweat. By way of non-limiting examples,these fragrances include those comprising middle note and/or top notevolatile constituents, like those selected from the group consisting ofallyl amyl glycolate, dihydromyrcenol, aldehyde C-12 MNA, decanol,isobornyl acetate, LILAL®, tricyclo decenyl acetate, benzyl salicylate,and the like, and combinations thereof.

Humectants

Humectant is also a desirable additional component which helpscontribute moisturizing properties in the compositions of the invention.Exemplary humectants can include, but are not limited to, polyhydricalcohols (i.e. 1,2-propanediol, 1,3 and 1,4-butanediol,2-methyl-1,3-propanediol, glycerine, and hexylene glycol) and polyols(i.e. polypropylene glycols, polyethylene glycols) and mixtures thereof.

Propellants

When the present invention involves the use of an aerosol composition, avolatile propellant is an essential component of such composition. Thelevel of incorporation of the volatile propellant is typically from 30to 99 parts by weight and particularly from 50 to 95 parts by weight.Non-chlorinated volatile propellant are preferred, in particularliquefied hydrocarbons or halogenated hydrocarbon gases (particularlyfluorinated hydrocarbons such as 1,1-difluoroethane and/or1-trifluoro-2-fluoroethane) that have a boiling point of below10.degree. C. and especially those with a boiling point below 0.degree.C. It is especially preferred to employ liquefied hydrocarbon gases, andespecially C3 to C6 hydrocarbons, including propane, isopropane, butane,isobutane, pentane and isopentane and mixtures of two or more thereof.Preferred propellants are isobutane, isobutane/isopropane,isobutane/propane and mixtures of isopropane, isobutane and butane.

Other propellants that can be contemplated include alkyl ethers, such asdimethyl ether or compressed non-reactive gases such air, nitrogen orcarbon dioxide.

Sensory Modifiers

Certain sensory modifiers are further desirable components in thecompositions of the invention. Such materials are preferably used at alevel of up to 20% by weight of a composition. Emollients, humectants,volatile oils, non-volatile oils, and particulate solids which impartlubricity are all suitable classes of sensory modifiers. Examples ofsuch materials include cyclomethicone, dimethicone, dimethiconol,isopropyl myristate, isopropyl palmitate, talc, finely divided silica(eg. Aerosil 200), polyethylene (eg. Acumist B18), polysaccharides, cornstarch, C12-C15 alcohol benzoate, PPG-3 myristyl ether, octyl dodecanol,C7-C14 isoparaffins, di-isopropyl adipate, isosorbide laurate, PPG-14butyl ether, glycerol, hydrogenated polyisobutene, polydecene, titaniumdioxide, phenyl trimethicone, dioctyl adipate, and hexamethyldisiloxane.

Thickening Agent (Including Thickeners and Gelling Agents)

The compositions of the present invention can also preferably comprise athickening agent, more preferably from about 0.1% to about 10%, evenmore preferably from about 0.1% to about 9%, and most preferably fromabout 0.25% to about 8%, of a thickening agent.

Preferred compositions of the present invention include a thickeningagent selected from carboxylic acid polymers, crosslinked polyacrylates,polyacrylamides, xanthan gum and mixtures thereof, more preferablyselected polyacrylamide polymers, xanthan gum and mixtures thereof.Preferred polyacrylamides are predispersed in a water-immiscible solventsuch as mineral oil and the like, containing a surfactant (HLB fromabout 7 to about 10) which helps to facilitate water dispersibility ofthe polyacrylamide. Most preferred for use herein is the non-ionicpolymer under the CTFA designation: polyacrylamide and isoparaffin andlaureth-7, available under the trade name Sepigel 305 from SeppicCorporation. Also useful are acrylic acid/ethyl acrylate copolymers andthe carboxyvinyl polymers sold by the B.F. Goodrich Company under thetrade mark of Carbopol resins. Suitable Carbopol resins are described inWO98/22085. All thickening agents discussed in application WO 00/24372should be considered as suitable for use in the present invention.

Also, Any gelling agent used in the art of soaps or deodorants may beused in the invention. These gelling agents are generally a metal saltof one or more fatty acids having a chain length of 12-22 carbon atoms.The fatty acid portion of the gelling agent is preferably a relativelypure saturated or unsaturated C12-C22 fatty acid including myristic,palmitic, stearic, oleic, linoleic, linolenic, and combinations thereof.Preferred gelling agents include sodium stearate, potassium stearate,sodium palmitate, potassium myristate, sodium myristate, combinationsthereof and the like.

Structurants

Structurants also may be additional component of the compositions of theinvention that are highly desirable in certain product forms.Structurants, when employed, are preferably present at from 1% to 30% byweight of a composition,

Suitable structurants include cellulosic thickeners such as hydroxypropyl cellulose and hydroxy ethyl cellulose, and dibenzylidenesorbitol. Other suitable structurants include sodium stearate, stearylalcohol, cetyl alcohol, hydrogenated castor oil, synthetic waxes,paraffin waxes, hydroxystearic acid, dibutyl lauroyl glutamide, alkylsilicone waxes, quaternium-18 bentonite, quaternium-18 hectorite,silica, and propylene carbonate.

Silicone Based Ingredients

The compositions of the present invention preferably also containsilicone based ingredients. Preferred examples are discussed below:

i) Silicone Based Emollients. Organopolysiloxane oils may be used asingredients with emollient benefits in the present compositions.Suitable organopolysiloxane oils include volatile, non-volatile, or amixture of volatile and non-volatile silicones. The term “non-volatile”as used in this context refers to those silicones that are liquid underambient conditions and have a flash point (under one atmospheric ofpressure) of or greater than about 100.degree. C. The term “volatile” asused in this context refers to those silicone oils having a flash pointof less than 100.degree. C. Suitable organopolysiloxanes can be selectedfrom a wide variety of silicones spanning a broad range of volatilitiesand viscosities. Non-volatile polysiloxanes are preferred. Suitablesilicones are disclosed in U.S. Pat. No. 5,069,897, issued Dec. 3, 1991,which is incorporated by reference herein in its entirety.

Preferred for use herein are organopolysiloxanes selected from the groupconsisting of polyalkylsiloxanes, alkyl substituted dimethicones,dimethiconols, polyalkylaryl siloxanes, and mixtures thereof. Morepreferred for use herein are polyalkylsiloxanes and cyclomethicones.Preferred among the polyalkylsiloxanes are dimethicones for exampleDC200 available from Dow Corning and SF96 available from GE Silicone.

ii) Silicone Based Emulsifiers. Preferred emulsions of the presentinvention include a silicone containing emulsifier or surfactant. A widevariety of silicone emulsifiers are useful herein. These siliconeemulsifiers are typically organically modified organopolysiloxanes, alsoknown to those skilled in the art as silicone surfactants. Usefulsilicone emulsifiers include dimethicone copolyols. These materials arepolydimethyl siloxanes which have been modified to include polyetherside chains such as polyethylene oxide chains, polypropylene oxidechains, mixtures of these chains, and polyether chains containingmoieties derived from both ethylene oxide and propylene oxide. Otherexamples include alkyl-modified dimethicone copolyols, i.e., compoundswhich contain C2-C30 pendant side chains. Still other useful dimethiconecopolyols include materials having various cationic, anionic,amphoteric, and zwitterionic pendant moieties.

Skin Lightening Agents

The compositions of the present invention can also comprise a skinlightening agent. When used, the compositions preferably comprise fromabout 0.1% to about 10%, more preferably from about 0.2% to about 5%,also preferably from about 0.5% to about 2%, of a skin lightening agent.Suitable skin lightening agents include those known in the art,including kojic acid, arbutin, ascorbic acid and derivatives thereof,e.g., magnesium ascorbyl phosphate. Further skin lightening agentssuitable for use herein also include those described in WO 95/34280 andWO 95/23780; each incorporated herein by reference.

Suncreens Inorganic Sunscreens

Inorganic sunscreens use titanium dioxide and zinc oxide. They workprimarily by reflecting and scattering UV light. The organics includewidely used ingredients such as octyl methoxycinnamate (OMC),4-methylbenzylidene camphor (4-MBC), avobenzone, oxybenzone, andhomosalate. They work primarily by absorbing UV light and dissipating itas heat.

Formulators often combine inorganic and organic sunscreens for asynergistic effect. In fact, that is how most are capable of achievingvery high SPF—sun protection factor—ratings. SPF is a measure of howeffectively a sunscreen in a formulation limits skin exposure to theUV-B rays that burn skin. The higher the number, the more protection asunscreen formula affords against sunburn.

Set forth below is a listing of approved sunscreen drug products forover-the-counter human use that are applicable for us in the inventionwhen used in combinations, formulation must follow FDA guidelines (21CFR 352 Sec. 352.10).

Active Limit, wt % a. Aminobenzoic acid (PABA) 15 b. Avobenzone 3 c.Cinoxate 3 d. Dioxybenzone 3 e. Ensulizole 4 f. Homosalate 15 g. Menthylanthranilate 5 h. Meradimate 5 i. Octinoxate 7.5 j. Octisalate 5 k.Octocrylene 10 l. Octyl methoxycinnamate 7.5 m. Octyl salicylate 5 n.Oxybenzone 6 o. Padimate O 8 p. Phenylbenzimidazole sulfonic acid 4 q.Sulisobenzone 10 r. Titanium dioxide 25 s. Trolamine salicylate 12 t.Zinc oxide 25

In addition to the organic sunscreens compositions of the presentinvention can additionally comprise inorganic physical sunblocks.Nonlimiting examples of suitable physical sunblocks are described inCTFA International Cosmetic Ingredient Dictionary, 6th Edition, 1995,pp. 1026-28 and 1103, Sayre, R. M. et al., “Physical Sunscreens”, J.Soc. Cosmet. Chem., vol 41, no 2, pp. 103-109 (1990). Preferredinorganic physical sunblocks are zinc oxide and titanium dioxide, andmixtures thereof.

When used, the physical sunblocks are present in an amount such that thepresent compositions are transparent on the skin (i.e., non-whitening),preferably less than or equal to about 5%. When titanium dioxide isused, it can have an anatase, rutile, or amorphous structure. Physicalsunblock particles, e.g., titanium dioxide and zinc oxide, can beuncoated or coated with a variety of materials including but not limitedto amino acids, aluminium compounds such as alumina, aluminium stearate,aluminium laurate, and the like; carboxylic acids and their salts e.g.,stearic acid and its salts; phospholipids such as lecithin; organicsilicone compounds; inorganic silicone compounds such as silica andsilicates; and mixtures thereof. A preferred titanium dioxide iscommercially available from Tayca (Japan) and is distributed by Tri-KIndustries (Emerson, N.J.) under the MT micro-ionised series (e.g., MT100SAS).

The compositions of the present invention preferably comprise from about0.1% to about 10%, more preferably from about 0.1% to about 4%, and mostpreferably from about 0.5% to about 2.5%, by weight, of inorganicsunscreen.

Esters

Esters can function as many of the above noted ingredients. While thosein those having skill in the art can readily determine which esters aremost appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

Natural Ingredients

Any natural or nature-derived ingredients similar in composition or infunction to the above ingredients can be used in these compositions.

Viscosity

Preferred compositions have an apparent viscosity of from about waterthin to about 1,000,000 mPa·s (centipoise). For example, preferredlotions have an apparent viscosity of from about 500 to about 25,000mPa·s; preferred creams have an apparent viscosity of from about 20,000to about 250,000 mPa·s.

Some personal care compositions containing Bio-PDO, such as clearshampoos and sulfate-free shampoo, may require approximately 30% lesssalt to adjust the viscosity than other compositions containingcomparable glycols such as propylene glycol, butylene glycol,2-methyl-1,3 propanediol etc. In other compositions such as bodywash—Bio-PDO may help maintain and build viscosity.

pH

The compositions of the present invention are usually formulated to havea pH of 9.5 or below and in general have a pH in the range from about4.5 to about 9, more preferably from about 5 to about 8.5. Somecompositions, particularly those comprising an additional active such assalicylic acid, require a lower pH in order for the additional active tobe fully efficacious. These compositions are usually formulated to havea pH of from about 2.5 to about 5, more preferably from about 2.7 toabout 4.

Skin Irritation and Sensitization

In a human skin patch test with approximately 100 subjects, 5, 25, and50% PDO did not cause any skin reactions indicative of irritation orsensitization. A second human skin patch test did not produce anyclinically significant dermal irritation or sensitization reactions withconcentrations of 25, 50, and 75% PDO at pH 7, or 75% PDO at pH 4 and 9.Based on these studies PDO is not expected to be a skin irritant orsensitizer in humans. In the second human skin patch test, propyleneglycol (1,2-propanediol or PG) was also tested at 25, 50, and 75% (pH 7)and all three concentrations of PG were patch test irritants andcumulative irritants for human skin.

Detergents

In detergent compositions, the glycol component typically is anemulsifier and/or phase stabilizer a hydrotrope/solvent or an enzymestabilizer.

Forms of the Composition

The composition of the invention can take a variety of physical formsincluding granular, gel, tablet, bar and liquid forms. Thesecompositions include a so-called concentrated granular detergentcomposition adapted to be added to a washing machine by means of adispensing device placed in the machine drum with the soiled fabricload.

Exemplary detergents include, but are not limited to, hand dish-washingdetergents; machine dish-washing detergents, including solid blockdetergents; solid laundry detergents, liquid laundry includinglight-duty liquid detergents (LDLD) and heavy-duty liquid detergents(HDLD); organic or inorganic clothing softeners, laundry bar soaps andcar wash detergent, among others.

The detergent compositions of the invention can comprise any form knownor used in the art, such as powders, liquids, granules, gels, pastes,tablets, small bags, bars, and double-partitioned containers, sprays orfoamed detergents and other homogenous or multi-phase daily detergentproduct forms. The products can be manually used or coated, and/or canbe used in a constant or freely variable amount of use, or by automaticcharge means, or can be used in electric products such as washingmachines. These products can have a wide range of pH of, e.g., from 2 to12 or more, and several tens gram-equivalent, per 100 g of theformulation, of NaOH may be added. These products can have a wide rangeof preliminary alkalinity. Both high suds and low suds detergents areincluded.

Light-Duty Liquid Detergents (LDLD) compositions include LDLDcompositions containing magnesium ions for improving surface activityand/or organic diamines and/or various foam stabilizers and/or sudsboosters, such as amine oxides and/or skin feeling improvers ofsurfactant and relaxing agents and/or enzyme types including protease,and/or sterilizers.

Heavy-Duty Liquid Detergents (HDLD) compositions include all ofso-called “structured” or multi-phase and “non-structured” or isotropicliquid types, and generally include aqueous or non-aqueous bleachingagents, and/or enzymes, or do not include bleaching agents and/orenzymes.

Heavy-duty granular detergents (HDGD) compositions include both of aso-called “compact” or coagulated, or non-spray dried type and aso-called “flocculated” or spray dried type. These compositions includeboth of a phosphate addition type and a phosphate non-addition type.Such detergents can include a type comprising a more general anionicsurfactant as a substrate, or may be a so-called “highly nonionicsurfactant” type comprising a generally nonionic surfactant held on anabsorbent, for example, in or on the surface of a zeolites or otherporous inorganic salt.

Softener (STW) compositions include various types of granular or liquidproducts that are softened by laundry, and can generally include organic(such as quaternary) or inorganic (such as clay) softeners.

Bar Soap (BS & HW) compositions include laundry bars and include both ofa type comprising a synthetic detergent and a soap as substrates and atype containing a softener. Such compositions include compositionsmanufactured by general soap manufacture techniques, such as pressuremolding, or techniques that are no so general, such as casting andabsorption of surfactant into a porous support. Other hand washdetergents are also included.

Fabric softeners (FS) include both of the conventional liquid andconcentrated liquid types and kinds to be added by dryers or supportedby a substrate. Other fabric softeners include those that are solid.

Special purpose cleaners (SPC) including the following products are alsoconsidered detergents for purposes of this invention: house-hold drydetergent modes, pre-treatment products of laundry bleaching agents,pre-treatment products for fabric protection, liquid higher fabricdetergent types, especially high suds products, liquid bleaching agentsincluding both of chlorine type and oxygen bleaching agent type,disinfectants, detergent aids, pre-treatment types including, forexample, bleaching additives and “stain-stick” or special sudsing typecleaners, and anti-fading treatment by sunlight.

Specialty household cleanser (SHC) including the following products arealso considered detergents for the purposes of this invention: allpurpose cleansing in the form of creams, gels, liquids, and floorcleaners; all-purpose sprays such as for cleaning glass surfaces; wipesincluding all-purpose wipes, glass cleaners, floor cleaners anddisinfectants; bathroom, shower and toilet cleaners; mildew cleaners andbleach.

The renewably-based, biodegradable 1,3-propanediol of the presentinvention is present in the aforementioned detergent compositions inamounts well known to those of ordinary skill in the appropriate art,typically up to about 25% by weight based on the weight of the totalcomposition.

A typical nonspecific detergent formulation may include, but is notlimited to, the following components by weight percent: 0.01-50.0%renewably-based, biodegradable 1,3-propanediol, 5.0-40.0% fatty acid andlower carbon number carboxylic acid esters, or mono and/or di-esters (asurfactant), and 1.0 to 70.0% of other surfactants or surfactant blends.Additionally, up to 5.0% by weight of the following components may beincluded: suds stabilizer/booster (preferred 1-10%), pH buffer(preferred 2-8%), enzymes, chelating agent, perfumes, builders,antioxidants, adjuvants, detersives.

A basic formula embodiment for a Light Duty Liquid Detergent (LDLD)product may include 0.1-70% of a surfactant, 0.1-20% of Bio-PDO and q.s.to 100% water. LDLDs are commonly used in dishwashing applications,including automatic, manual, dishwasher rinses, plastic stain removers,pots & pans cleaners, pre-treatments and water softeners.

A basic formula embodiment for a Heavy Duty Liquid Detergent (HDLD)product may include 0.1-50% of a surfactant, 0.1-20% of Bio-PDO and q.s.to 100% water. HDLDs are commonly used in laundry applications,including laundry products containing bleach, hypo-allergenics,phosphate-free materials, dry cleaning materials, fabric conditioners,fabric enhancers, fabric finishes, fabric sizing, fabric softeners,pre-washes, stain removers and starches.

A basic formula embodiment for a Liquid Automatic Dishwasher Detergent(LADD) product may include 0.1-30% of a builder, 0.1-17% of acaustic/Bleach, 0.1-20% of Bio-PDO and q.s. to 100% of water.Applications include dishwash, liquid Pre-spotters, rinse aids,phosphate-free materials, hypochlorite-free materials and enzymes.

A basic formula embodiment for a specialty household cleanser (SHC) mayinclude 0.1-70% of a surfactant, 0.1-50% of Bio-PDO, and q.s. to 100%water. Specific applications include, all purpose cleansing in the formof creams, gels, liquids, and floor cleaners; all-purpose sprays such asfor cleaning glass surfaces; wipes including all-purpose wipes, glasscleaners, floor cleaners and disinfectants; bathroom, shower and toiletcleaners; mildew cleaners and bleach.

Detergent Components

Detergent compositions of the invention can contain from 0.01 to 99% byweight of one or more of any of the following general auxiliarycomponents: builders, surfactants, enzymes, polymers, bleaching agents,bleach surfactants, catalyst components, various active components orspecial components such as dispersant polymers, color speckles, silverprotecting agents, anti-fogging agents and/or corrosion inhibitors,dyes, fillers, sterilizers, alkaline agents, hydrotropic agents,antioxidants, enzyme stabilizers, pro-perfumes, perfumes, plasticizers,carriers, processing aids, pigments, and solvents for liquidformulations.

In general, detergent components are included for converting acomposition containing only the minimum essential components into acomposition useful for the desired detergent purpose. It is recognizedthat those skilled in the art can readily determine which detergentcomponents are required for desired detergent applications.

The precise nature of these additional components, and levels ofincorporation thereof, will vary depending upon the physical form of thecomposition and the nature of the cleaning operation for which it is tobe used.

Detergent Surfactants

The detergent compositions of the invention may contain any knowndetergent surfactant, and such surfactants are well known to thosehaving skill in the art. Specifically, detergent surfactants of theinvention can include anionic, nonionic, zwitter-ionic or amphoteric,betaine, and diamine are, surfactants that are known to be useful indetergent applications.

In all of the detergent surfactants, the chain length of the hydrophobicmoiety is typically in the general range of from C8 to C20, andespecially in the case of laundering with cold water, the chain lengthis often preferably in the range of from C8 to C18.

Detergent Enzymes

The detergent composition of the invention may use enzymes for variouspurposes such as removal of protein-based, carbohydrate-based, ortriglyceride-based soils from substrates, transfer inhibition of refugeedyes in fabric laundering, and fabric restoration. “Detergent enzymes”as used herein mean all enzymes having advantageous effects in washing,soil removal, and others in laundering.

Builders

Builder compositions are preferably those that control the hardness ofminerals in washing water, especially Ca and/or Mg, thus simplifying theremoval and/or dispersal of granular soils from the surface, while alsooptionally imparting an alkaline agent and/or buffering action. Ingranular or powder detergents, the builder may function as an absorbentfor the surfactant. Alternatively, some compositions can be formulatedin a completely water-soluble form, which may be either organic orinorganic, depending on the intended utility.

Suitable silicate builders include water-soluble types and hydratedsolid types, and include other kinds such as those having a chain, layeror steric structure, amorphous solid silicates, and those as preparedsuch that they are used as not particularly structured liquiddetergents.

Aluminosilicate builders, so-called zeolites, are particularly useful ingranular detergents, but can be incorporated into pastes or gels. Thealuminosilicates may be crystalline or amorphous, or may be natural orsynthetic.

For the purpose of making it easy to control the hardness of minerals inthe washing water, especially Ca and/or Mg, or of making it easy toremove granular solids from the surface, the composition of theinvention may optionally contain detergent builders in place of or inaddition to the foregoing silicates and aluminosilicates. The builderscan be made to function in various mechanisms so as to form soluble orinsoluble complexes with mineral ions by ion exchange or by providingmineral ions with the surface more adherent than the surface of thematerial to be cleaned. The amount of the builder can be varied widelydepending on the final utility and physical form of the composition.

Here, suitable builders can be selected from the group consisting ofphosphates and polyphosphates, especially sodium salts, carbonates,bicarbonates, sodium carbonate, organic mono-, di-, tri-, andtetracarboxylates, especially water-soluble non-surfactant carboxylatesin acid, sodium, potassium or alkanolammonium forms, and aliphatic andaromatic type-containing oligomers or water-soluble low-molecularpolymer carboxylates. For example, for the purpose of pH buffer, thesebuilders can be complemented by all of fillers or carriers that areimportant in the techniques of detergent compositions including boratesor sulfates, especially sodium sulfate, and other stabilized surfactantsand/or builders.

In the invention, builder mixtures can be used. In general, the buildermixture optionally comprises two or more usual builders, and iscomplemented by a chelating agent, a pH buffer, or a filler.

Examples of phosphorus-containing builders include polyphosphates,represented by tripolyphosphates, pyrophosphates, and glassy polymermetaphosphates, of alkali metals and ammonium and alkanolammoniums, andphosphonates.

Suitable carbonate builders include carbonates of an alkaline earthmetal or an alkali metal, inclusive of carbonate minerals such as sodiumbicarbonate and sodium carbonate, complex salts of sodium carbonate orpotassium carbonate, and calcium carbonate.

As described herein, the “organic detergent builders” suitable for theuse along with the alkylaryl sulfonate surfactant includepolycarboxylate compounds including water-soluble non-surfactantdicarboxylates and tricarboxylates. More generally, the builderpolycarboxylate has plural carboxylate groups, preferably at least threecarboxylates. The carboxylate builder can be incorporated in an acidicor partially neutral, neutral or excessively basic form. In the case ofthe salt form, salts of alkali metals such as sodium, potassium, andlithium, or alkanolammonium salts are preferred. The polycarboxylatebuilder includes ether polycarboxylates.

Nitrogen containing builders including amino acids such as lysine, orlower alcohol amines like mono, di-, and tri-ethanolamine,try(hydroxymethyl)amino methane, 2-amino-2-methylpropanol, and disodiumglutamate.

Citric acid salts such as citric acid and soluble salts thereof are apolycarboxylate builder important for, for example, heavy-duty liquiddetergents (HDL) because they are available from resources that can beregenerated and are biodegradable. The citric acid salts can also beused in granular compositions especially in combination of zeolitesand/or layered silicates. Oxydisuccinic acid salts are especially usefulin such compositions and combinations.

In the detergent composition of the invention, any builders known inthis field can be incorporated generally in an amount of from about 0.1to about 50% by weight, more preferably 0.5 to 30% by weight and mostpreferably 1 to 25% by weight.

Oxygen Bleaching Agents

In one embodiment, the invention comprises an “oxygen bleaching agent”as a part or whole of the detergent composition. Any known oxidizingagents can be used. Alternatively, oxidizing agent bleaching agents suchas systems of generating hydrogen peroxide by oxygen or an enzyme, orhypohalogenic acid salts, for example, chlorine bleaching agents such ashyposulfites, can also be used.

Examples of peroxide-based general oxygen bleaching agents includehydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates, andorganic peroxy acids including hydrophilic or hydrophobic mono- ordi-peroxy acids. These components may be peroxycarboxylic acids,perpoxyimide acids, amidoperoxycarboxylic acids, or salts thereofincluding their calcium, magnesium or mixed cationic salts. Variouskinds of peracids can be used in a liberated form or as precursormaterials called “bleach surfactant” or “bleach promoters”, whichrelease peracids corresponding to hydrolysis in the case of acombination with a supply source of hydrogen peroxide.

Inorganic peroxides, suproxides, organic hydroperoxides such as cumenehydroperoxide and t-butyl hydroperoxide, and inorganic peroxo acids andsalts thereof, such as peroxosulfates, are also useful as the oxygenbleaching agent.

Mixed oxygen bleaching agent systems are generally effective as inmixtures of oxygen bleaching agents with known bleach surfactant,organic catalysts, enzyme catalysts, or mixtures thereof. Further, thesemixtures can further contain brighteners, light bleaching agents, anddye transfer inhibitors of types that are well known in this field.

Hydroperoxides and peroxohydrates are organic salts, or more generally,inorganic salts that can readily release hydrogen peroxide. Theperoxohydrates are a general example of a “hydrogen peroxide source” andinclude perborates, percarbonates, perphosphates, and persilicates.Preferred peroxohydrates include all of sodium carbonate hydroperoxideand equivalent commercially available “percarbonate” bleaching agents,and so-called sodium perborate hydrates, and sodium pyrophosphatehydroperoxide can also be used. Urea hydroperoxides are also useful asthe peroxohydrate.

There are included inorganic peroxohydrates, organic peroxohydrates,hydrophilic or hydrophobic mono- or diperacids, organic peracidsincluding peroxycarboxylic acids, peroxyimide acids, andamidoperoxycarboxylic acids, salts of calcium, magnesium, or mixedcationic salts.

In the detergent composition of the invention, any oxygen bleachingagents are added in such formulations preferably in ranges from about 0to 15%, and most preferably from about 0.2 to 12%

Bleach Surfactant can be used as well. Examples of useful bleachsurfactants include amides, imides, esters, and acid anhydrides.Generally, in such bleach surfactants, there is present at least onesubstituted or unsubstituted acyl moiety having a leaving group in thestructure, R—C(O)-L. One alternative method of use comprises acombination of the bleach surfactant with a hydrogen peroxide supplysource such as perborates and percarbonates. One or more peracid-formingmoieties or leaving groups can be present. Mixtures of bleachsurfactants can be also used.

The bleach surfactant can be used in an amount of up to 20% by weight,and preferably from 0.1 to 10% by weight of the composition. For theform of highly concentrated bleaching agent additive products or theform in which the bleach surfactant is used in an automatic chargedevice, it can be used in an amount of 40% by weight or more.

Transition Metal Bleaching Agent Catalysts can also be used in theinvention. For example, manganese compounds can be optionally used asthe bleaching compound to have a catalytic action. As useful cobaltbleaching catalysts, ones that are known may be used.

In addition to the above-enumerated bleach surfactant, Enzyme-BasedSupply Sources of Hydrogen Peroxide. For instance, suitable hydrogenperoxide generating mechanisms include combinations of C1 to C4 alkanoloxidases and C1 to C4 alkanols, especially a combination of methanoloxidase (MOX) and ethanol. Bleaching-related other enzymatic materialssuch as peroxidases, haloperoxidases, and oxidases, superoxide moleculardisplacement enzymes, catalases, and their reinforcing agents, or moregenerally, inhibitors can be optionally used in the composition.

Oxygen Transfer Agents and Precursors

All known organic bleaching agent catalysts, oxygen transfer agents, orprecursors thereof are also useful herein. These materials include theircompounds themselves and/or precursors thereof, such as all of ketonessuitable for manufacture of dioxiranes, and/or dixoirane precursors orall different atom-containing analogues of dioxiranes. As preferredexamples of such components, are especially included hydrophilic orhydrophobic ketones that manufacture the dioxiranes on the spot, alongwith monoperoxysulfate. Examples of such oxygen bleaching agents thatare preferably used along with the oxygen transfer agent or precursorinclude percarboxylic acids and salts, percarbonic acids and slats,peroxy monosulfuric acid and salts, and mixtures thereof.

Polymeric Soil Releasing Agents

The composition of the invention can optionally comprise one or moresoil releasing agents. The polymeric soil releasing agent ischaracterized by having hydrophilic segments to hydrophilize the surfaceof hydrophobic fibers such as polyester and nylon and hydrophobicsegments to deposit upon hydrophobic fibers and remain adhered theretothrough completion of the laundry cycle to function as an anchor for thehydrophilic segments. This can enable stains occurring sequent totreatment with the soil releasing agent to be more easily cleaned inlater washing procedures.

In the case of the use, the soil releasing agent generally accounts forfrom about 0.01 to about 10% by weight of the composition.

Clay Soil Removal/Anti-Redeposition Agents

The composition of the invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andanti-redeposition properties. Granular detergent compositions containingthese compounds typically contain from about 0.01% to about 10.0% byweight of the water-soluble ethoxylated amines, and liquid detergentcompositions typically contain about 0.01% to about 5% by weight of thewater-soluble ethoxylated amines.

Preferred soil release and anti-redeposition agents are ethoxylatedtetraethylenepentamine. Other preferred soil releaseremoval/anti-redeposition agents are ethoxylated amine polymers,zwitter-ionic polymers, and amine oxides. Other soil release removaland/or anti-redeposition agents that are known in this field can also beused in the composition of the invention. Another type of the preferredanti-redeposition agent includes carboxy methyl cellulose (CMC)-basedcomponents.

Polymeric Dispersing Agents

Polymeric dispersing agents can be effectively used in an amount of fromabout 0.01 to about 10% by weight of the composition of the inventionespecially in the presence of zeolite and/or layered silicate builders.Suitable polymeric dispersing agents include polymeric polycarboxylatesand polyethylene glycols, although others known in the art can also beused. It is believed that polymeric dispersing agents enhance overalldetergent builder performance, when used in combination with otherbuilders (including lower molecular weight polycarboxylates) by crystalgrowth inhibition, particulate soil release, peptization, andanti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidforms. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarobyxlates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid, and methylenemalonic acid.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers that are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 1,000 to 500,000, more preferably from about 2,000 to250,000, and most preferably from about 3,000 to 100,000. Water-solublesalts of such acrylic acid polymers can include, for example, the alkalimetal, ammonium and substituted ammonium salts.

Acrylic acid/maleic acid-based copolymers may also be used as apreferred component of the dispersing/anti-redeposition agent. Suchmaterials include the water-soluble salts of copolymers of acrylic acidand maleic acid. The average molecular weight of such copolymers in theacid form preferably ranges from about 2,000 to 100,000, more preferablyfrom about 3,000 to 80,000, and most preferably from about 4,000 to70,000. The ratio of acrylate to maleate segments in such copolymersgenerally ranges from about 9:1 to about 1:9, and more preferably fromabout 8:2 to 3:7. Water-soluble salts of such acrylic acid/maleic acidcopolymers can include, for example, the alkali metal, ammonium andsubstituted ammonium salts.

Copolymers of acrylic acid and/or maleic acid and a polyalkylene glycolcan also be used as a preferred component of thedispersing/anti-redeposition agent. The copolymers are preferably graftpolymers of acrylic acid and/or maleic acid and a polyalkylene glycol,copolymers of acrylic acid and/or maleic acid and an alkylene oxideadduct of allyl alcohol or isoprenol, and copolymers of acrylic acidand/or maleic acid and a polyalkylene glycol acrylate or methacrylate,and more preferably graft polymers of acrylic acid and/or maleic acidand a polyalkylene glycol and copolymers of acrylic acid and/or maleicacid and an alkylene oxide adduct of allyl alcohol or isoprenol.

The average molecular weight of the copolymers preferably ranges fromabout 2,000 to 100,000, more preferably from about 3,000 to 80,000, andmost preferably from about 4,000 to 70,000.

Acrylic acid/acrylamide based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. The averagemolecular weight of such copolymers in the acid form preferably rangesfrom about 3,000 to 100,000, more preferably from about 4,000 to 20,000,and most preferably from about 4,000 to 10,000. The acrylamide contentin such copolymers generally is less than about 50%, preferably lessthan about 20%, and most preferably about 1 to about 15%, by weight ofthe polymer.

Another polymeric component that can be incorporated is polyethyleneglycol (PEG). PEG can exhibit dispersing agent performance as well asact as a clay soil removal/anti-redeposition agent. Typical molecularweight ranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, and more preferably fromabout 1,500 to about 10,000.

Polyasparatate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolites builders. Dispersing agents suchas polyasparatate preferably have a (weight average) molecular weight ofabout 10,000.

In the detergent composition of the invention, Polymeric DispersingAgents known in this field can be incorporated generally in an amount offrom about 0.01 to about 15%, more preferably from 0.05 to 10%, thenmost preferably 0.1 to 5%.

Brighteners

In the detergent composition of the invention, any optical brightenersor other brightening or whitening agents known in this field can beincorporated generally in an amount of from about 0.01 to about 1.2% byweight. Such optical brighteners are often used in the case where thedetergent is designed for fabric washing or processing applications.

Polymeric Dye Transfer Inhibiting Agents

The composition of the invention may also include one or more materialseffective for inhibiting the transfer of dyes from one fabric to anotherduring the cleaning process. Generally, such dye transfer inhibitingagents include polyvinylpyrrolidone polymers, polyamide N-oxidepolymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents generally comprise from about 0.01 to about 10% by weight,preferably from about 0.01 to about 5° k by weight, and more preferablyfrom about 0.05 to about 2% by weight of the composition.

The optical brightener selected for use in the invention exhibitsespecially effective dye transfer inhibition performance benefits whenused in combination with the polymeric dye transfer inhibiting agent.The combination of such selected polymeric materials with such selectedoptical brightener provides significantly better dye transfer inhibitionin aqueous wash solutions than does either of these two detergentcomposition components when used alone.

Chelating Agents

The detergent composition of the invention may also optionally containone or more chelating agents, especially chelating agents for transitionmetal coming from others. The transition metals generally seen inwashing solutions include water-soluble, colloidal or granular ironand/or manganese and may sometimes associate as oxides or hydroxides.Preferred chelating agents are chelating agents that effectively inhibitsuch transition metals, especially inhibit such transition metals ortheir compounds to adhere to fabrics, and/or inhibit non-preferred redoxreaction occurred in the washing medium and/or on the interface of thefabric or hard surface. The general chelating agents can be selectedfrom the group consisting of amino carboxylates, amino phosphates,polyfunctionally-substituted aromatic chelating agents, and mixturesthereof.

The composition of the invention may also contain water-soluble methylglycine diacetic acid salts as a chelating agent that can effectively beused together with insoluble builders such as zeolites and layeredsilicates.

If utilized, the chelating agent generally accounts for from about 0.1to about 15% by weight of the composition. More preferably, if utilized,the chelating agent accounts for from about 0.1 to about 3.0% by weight.

Suds Suppressors

In the case where washing is required in intended utilities, especiallywashing by washing machines, compounds for reducing or suppressing theformation of suds can be incorporated into the composition of theinvention. For other compositions, for example, compositions as designedfor hand washing, high sudsing may be desired, and such components canbe omitted. Suds suppression can be of particularly importance in theso-called “high concentration cleaning process” and in front-loadingEuropean-style washing machines (so-called drum type washing machines).

A very wide variety of materials may be used as suds suppressors. Thecomposition of the invention generally comprises from 0% by weight toabout 10% by weight of suds suppressors.

Fabric Softeners

Various through-the-wash fabric softeners can optionally be used in anamount of from about 0.5 to about 10% by weight to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners. Further, inthe cleaning process of the invention, known fabric softeners includingthose of biodegradation type can be used in modes including thepre-treatment, main cleaning, post-laundry, and addition into washingmachines and dryers.

Perfumes

Perfumes and perfumery ingredients useful in the compositions andprocesses comprise a wide variety of natural and synthetic chemicalingredients, including, but not limited to, aldehydes, ketones, andesters. Also, included are various natural extracts and essences thatcan comprise complex mixtures of ingredients such as orange oil, lemon,oil, rose extract, lavender, musk, patchouli, balsamic essence,sandalwood oil, pine oil, and cedar. Finished perfumes typicallycomprise from about 0.01 to about 2% by weight of the detergentcomposition, and individual perfumery ingredients can comprise fromabout 0.0001 to about 90% by weight of a finished perfume composition.

Esters

Esters can function as many of the above noted ingredients. While thosein those having skill in the art can readily determine which esters aremost appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

Other Components

A wide variety of other ingredients useful in detergent compositions canbe included in the composition, including other ingredients, carriers,hydrotropes, processing aids, dyes or pigments, solvents for liquidformulations, and soil fillers for bar compositions. If high sudsing isdesired, suds boosters such as C10 to C16 alkanolamides can beincorporated into the composition, typically in an amount of from 1% byweight to 10% by weight C10 to C14 monoethanol and diethanol amidesillustrate a typical class of such suds boosters. Use of such sudsboosters with high sudsing adjuvant surfactants such as the amineoxides, betaines and sultanines noted above is also advantageous. Ifdesired, water-soluble magnesium and/or calcium salts can be addedtypically in an amount of from 0.1% by weight to 2% by weight, toprovide additional suds.

Various detergent ingredients employed in the composition can optionallybe further stabilized by absorbing the ingredients onto a poroushydrophobic substrate, then coating the substrate with a hydrophobiccoating. Preferably, the detergent ingredient is admixed with asurfactant before being absorbed into the porous substrate. In use, thedetergent ingredient is released from the substrate into the aqueouswashing liquor, where it performs its intended detergent function.

The liquid detergent composition can contain water and other solvents asdiluents. Low-molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for stabilizing the surfactant, but polyols suchas those having from 2 to about 6 carbon atoms and from 2 to about 6hydroxyl groups (such as 1,3-propanediol, ethylene glycol, glycerin, andpropylene glycol) can also be used. The composition can contain suchdiluents in an amount of from 5% by weight to 90% by weight, andpreferably from 10% by weight to 50% by weight.

The detergent composition is preferably formulated such that, during usein aqueous cleaning operations, the wash water has a pH of from about6.5 to about 12.5, preferably from 7 to 12, and more preferably fromabout 7.0 to about 11. Laundry products are typically at a pH of from 9to 11. Techniques for controlling the pH at recommended usage levelsinclude the use of buffers, alkalis, acids, etc.

The detergent compositions of the invention can contain any naturalingredients where appropriate. Natural ingredients include any naturalor nature-derived ingredients similar in composition or in function toany of the ingredients listed above.

Liquid Laundry Detergents

While the following listing of ingredients is particularly suited forliquid laundry detergents, it is clearly within the scope of one havingskill in the art to determine whether such ingredients may be useful forother detergent applications.

Bio-PDO is preferably provided in liquid laundry detergents atconcentration ranges of about 0.1% to about 25%, more preferably about0.5% to about 20% and most preferably about 1% to about 15%

Thickeners

The physical stability of the liquid product may be improved and thethickness of the liquid product may be altered by the addition of across linking polyacrylate thickener to the liquid detergent product asa thixotropic thickener.

PH Adjusting Components

The above liquid detergent product is preferably low foaming, readilysoluble in the washing medium and most effective at pH values bestconducive to improved cleaning performance, such as in a range ofdesirably from about pH 6.5 to about pH 12.5, and preferably from aboutpH 7.0 to about pH 12.0, more preferably from about pH 8.0 to about pH12.0, and most preferably, less than about 9.0 pH The pH adjustingcomponents are desirably selected from sodium or potassium hydroxide,sodium or potassium carbonate or sesquicarbonate, sodium or potassiumsilicate, boric acid, sodium or potassium bicarbonate, sodium orpotassium borate, and mixtures thereof. NaOH or KOH are the preferredingredients for increasing the pH to within the above ranges. Otherpreferred pH adjusting ingredients are sodium carbonate, potassiumcarbonate, and mixtures thereof.

Low Foaming Surfactant

The liquid nonionic surfactant detergents that can be used to practicethe present invention are preferably are alkyl ethoxylates innon-chlorine bleach liquid ADW compositions. One example of anon-chlorine bleach stable surfactant is SLF18® manufactured by BASFCorporation. Alternatively, in chlorine bleach containing liquid ADWcompositions, chlorine bleach stable low foaming surfactants arepreferred and such surfactants are present in a range of from about 0.1%to about 10% by weight of the liquid composition. Such surfactants aregenerally known to one skilled in the art and need not be elaboratedhere, for purposes of brevity. An example of a chlorine bleach stablesurfactant is Dowfax® anionic surfactant available from the Dow ChemicalCompany.

Examples of the nonionic surfactant include polyoxyalkylene alkylethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitanesters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylenesorbitol fatty acid esters, polyoxyalkylene glycerin fatty acid esters,monoglycerides, sorbitan fatty acid esters, fatty acidmonoethanolamides, fatty acid diethanolamides and alkyl polyglucosides.

Examples of the amphoteric surfactants include acetic acid betaines,amidoacetic acid betaines, sulfobetaines, amidosulfobetaines,phosphobetaines, alkylamine oxides, and amidoamine oxides. Of these,fatty acid amidopropylbetaines such as cocamidopropyl betaine andlauramidopropyl betaine are preferred. Include imidazoline derivedamphoterics: disodium cocoa amphodiproprionate.

Two or more of these surfactants may be used in combination. Thesurfactant is preferably contained in an amount of from 5 to 50 wt. %,more preferably from 10 to 30 wt. %, even more preferably from 10 to 20wt. % based on the detergent composition of the present invention, fromthe viewpoints of foaming property, liquid properties during use anddetergency.

Silicones

The detergent composition of the present invention may contain siliconesfor further improvement in the conditioning effects. The siliconesinclude dimethylpolysiloxanes (viscosity: 5 mm.sup.2/s to 20 millionmm.sup.2/s), amino-modified silicones, polyether-modified silicones,methylphenylpolysiloxanes, fatty acid-modified silicones,alcohol-modified silicones, alkoxy-modified silicones, epoxy-modifiedsilicones, fluorine-modified silicones, cyclic silicones andalkyl-modified silicones, of which dimethylpolysiloxanes are preferred.The content of the silicone in the detergent composition of the presentinvention is preferably from 0.01 to 10 wt. %. The detergent compositionof the present invention may contain other conditioning components suchas a cationic polymer (cationic cellulose, cationic guar gum, or thelike). Their content in the detergent composition of the presentinvention is preferably from 0.1 to 5 wt. %.

General Liquid Components

The detergent composition of the present invention may contain, inaddition, components employed ordinarily for detergent compositionsaccording to the intended use. Examples of such components includehumectants such as propylene glycol, glycerin, diethylene glycolmonoethyl ether, sorbitol and panthenol; colorants such as dyes andpigments; viscosity regulators such as methyl cellulose, polyethyleneglycol and ethanol; plant extracts; antiseptics; bactericides; chelatingagents; vitamin preparations; anti-inflammatory agents; perfumes;ultraviolet absorbers; and antioxidants.

Solid and Semi-Solid Laundry Detergents

While the following listing of ingredients is particularly suited forsolid laundry detergents, it is clearly within the scope of one havingskill in the art to determine whether such ingredients may be useful forother detergent applications.

The solid laundry detergent compositions of the invention comprises aratio of Bio-PDO to binder portion in the range of 1:20 to 20:1, byweight percentage; preferably in the range of from 1:5 to 5:1, and mostpreferably from 1:2 to 2:1 therefore 0.1 to 25%, 0.5 to 15%, 1 to 10%from about 0.001 wt % to about 0.5 wt %, more preferably from about 0.1wt % to about 0.25 wt %, and most preferably from about 0.25 wt % toabout 0.1 wt % bio-PDO.

Preferably, the detergent composition has a particle size distributionsuch that no more than 10 wt % by weight of the composition, has aparticle size greater than 850 micrometers, and no more than 10 wt % byweight of the composition, has a particle size less than 250micrometers.

The composition optionally comprises one or more adjunct components. Theadjunct components are typically selected from the group consisting ofother anionic surfactants, cationic surfactants, non-ionic surfactants,zwitterionic surfactants, other builders, polymeric co-builders such aspolymeric polycarboxylates, bleach, other hydrotropes, chelants,enzymes, anti-redeposition polymers, soil-release polymers, polymericsoil-dispersing and/or soil-suspending agents, dye-transfer inhibitors,fabric-integrity agents, fluorescent whitening agents, suds suppressors,fabric-softeners, flocculants, cationic fabric-softening components,perfumes and combinations thereof.

A suitable adjunct component may be an anionic surfactant other than thealkyl alkoxylated sulphate surfactant and the linear alkyl benzenesulphonate surfactant. Suitable other anionic surfactants are branchedor linear C.sub.8-C.sub.18 alkyl sulphate surfactants. An especiallysuitable other anionic surfactants are methyl branched C.sub.8-C.sub.18alkyl sulphate surfactants.

A suitable adjunct component may be an anionic surfactant other than thealkyl alkoxylated sulphate surfactant and the linear alkyl benzenesulphonate surfactant. Suitable other anionic surfactants are branchedor linear C.sub.8-C.sub.18 alkyl sulphate surfactants. An especiallysuitable other anionic surfactants are methyl branched C.sub.8-C.sub.18alkyl sulphate surfactants.

A suitable adjunct component may be a hydrotrope other than thealkoxylated alkyl alcohol. Suitable hydrotropes include sodium cumenesulphate, sodium toluene sulphate and sodium xylene sulphate.

Gel Detergents

While the following listing of ingredients is particularly suited forgel detergents, it is clearly within the scope of one having skill inthe art to determine whether such ingredients may be useful for otherdetergent applications. Auto-dish washing formulations are most commonlyused in gel form.

Bio-PDO is preferably provided in liquid laundry detergents atconcentration ranges of about 0.1% to about 25%, more preferably about0.5% to about 20% and most preferably about 1% to about 15%.

Preferably, the lamellar-phase gel laundry composition of the inventioncomprises from 1 to 8%, more preferably from 3 to 6%, by weight of agelling agent.

Such a gelling agent may suitably be a fatty alcohol having the formulaR.sub.1-(CHOH)-R.sub.2, wherein R.sub.1, R.sub.2 are independentlyselected from hydrogen and saturated or unsaturated, linear or branched,C.sub.1-C.sub.16 alkyl groups, whereby the total number of carbon atomsin the fatty alcohol is between 8 and 17.

Preferably a fatty alcohol gelling agent is used that has the aboveformula, wherein R.sub.1 is hydrogen and R.sub.2 is selected fromsaturated or unsaturated, linear or branched C.sub.9-C.sub.13 alkylgroups. Favorable results could generally be obtained when applying asgelling agent a fatty alcohol in which the total chain length is similarto the average chain length of the surfactants present in theformulation. Such a gelling agent is preferably selected from the groupconsisting of 1-decanol, 1-dodecanol, 2-decanol, 2-dodecanol,2-methyl-1-decanol, 2-methyl-1-dodecanol, 2-ethyl-1-decanol, andmixtures thereof. Commercially available materials that are particularlysuitable for use as gelling agent include Neodol 23 or Neodol 25produced by Shell Chemical Co., Exxal 12 or Exxal 13 produced byExxonmobil Chemical Co. and Isalchem 123 or Lialchem 123 produced bySasol Chemical Co.

The gelling agent may also suitably be a non-neutralised fatty acidhaving the formula R₃—(COON)—R₄, wherein R₃ and R₄ are independentlyselected from hydrogen and saturated or unsaturated, linear or branchedC₁-C₂₂ alkyl groups, whereby the total number of carbon atoms in thefatty acid is between 10 and 23. Such a fatty acid gelling agent ispreferably selected from oleic acid, lauric acid, myristic acid,palmitic acid, stearic acid, linoleic acid, linolenic acid and mixturesthereof.

Furthermore, the gelling agent may suitably be a naturally obtainablefatty acid selected from tallow, coconut, and pal kernel fatty acids.

Anionic Surfactant

The anionic surfactant that may be present in the gel composition of theinvention is preferably selected from the group consisting of linearalkyl benzene sulphonates, alkyl sulphonates, alkylpolyether sulphates,alkyl sulphates and mixtures thereof.

Nonionic Surfactant

The surfactant system in the gel composition of the invention may alsocontain a nonionic surfactant.

Nonionic detergent surfactants are well-known in the art. They normallyconsist of a water-solubilizing polyalkoxylene or a mono- ord-alkanolamide group in chemical combination with an organic hydrophobicgroup derived, for example, from alkylphenols in which the alkyl groupcontains from about 6 to about 12 carbon atoms, dialkylphenols in whichprimary, secondary or tertiary aliphatic alcohols (or alkyl-cappedderivatives thereof), preferably having from 8 to 20 carbon atoms,monocarboxylic acids having from 10 to about 24 carbon atoms in thealkyl group and polyoxypropylene. Also common are fatty acid mono- anddialkanolamides in which the alkyl group of the fatty acidradicalcontains from 10 to about 20 carbon atoms and the alkyloyl group havingfrom 1 to 3 carbon atoms. In any of the mono- and di-alkanolamidederivatives, optionally, there may be a polyoxyalkylene moiety joiningthe latter groups and the hydrophobic part of the molecule.

Builders

Builders in this embodiment that may be used according to the presentinvention include conventional alkaline detergent builders, inorganic ororganic, which can be used at levels of from 0% to 50% by weight of thegel composition, preferably from 1% to 35% by weight.

Examples of suitable inorganic detergency builders that may be used arewater soluble alkali metal phosphates, polyphosphates, borates,silicates, and also carbonates and bicarbonates. Specific examples ofsuch builders are sodium and potassium triphosphates, pyrophosphates,orthophosphates, hexametaphosphates, tetraborates, silicates, andcarbonates.

Examples of suitable organic detergency builders are: (1) water-solubleamino polycarboxylates, e.g. sodium and potassiumethylenediaminetetraacetates, nitrilotriacetates and N-(2hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid,e.g. sodium and potassium phytates; (3) water-soluble polyphosphonates,including specifically sodium and potassium salts ofethane-1-hydroxy-1,1-diphosphonic acid; sodium and potassium salts ofmethylene diphosphonic acid; sodium and potassium salts of ethylenediphosphonic acid; and sodium and potassium salts ofethane-1,1,2-triphosphonic acid.

In addition, polycarboxylate builders can be used satisfactorily,including water-soluble salts of mellitic acid, citric acid, andcarboxymethyloxysuccinic acid, salts of polymers of itaconic acid andmaleic acid, tartrate monosuccinate, and tartrate disuccinate.

Desirably, the detergency builder is selected from the group consistingof carboxylates, polycarboxylates, aminocarboxylates, carbonates,bicarbonates, phosphates, phosphonates, silicates, borates and mixturesthereof.

Alkalimetal (i.e. sodium or potassium) citrate is most preferred buildermaterial for use in the invention.

Amorphous and crystalline zeolites or aluminosilicates can also besuitably used as detergency builder in the gel composition of theinvention.

Enzymes

Suitable enzymes for use in the present embodiment of the inventioninclude proteases, amylases, lipases, cellulases, peroxidases, andmixtures thereof, of any suitable origin, such as vegetable, animalbacterial, fungal and yeast origin. Preferred selections are influencedby factors such as pH-activity, thermostability, and stability to activebleach detergents, builders and the like. In this respect bacterial andfungal enzymes are preferred such as bacterial proteases and fungalcellulases.

Enzymes are normally incorporated into detergent composition at levelssufficient to provide a “cleaning-effective amount”. The term “cleaningeffective amount” refers to any amount capable of producing a cleaning,stain removal, soil removal, whitening, or freshness improving effect onthe treated substrate. In practical terms for normal commercialoperations, typical amounts are up to about 5 mg by weight, moretypically 0.01 mg to 3 mg, of active enzyme per gram of detergentcomposition. Stated otherwise, the composition of the invention maytypically comprise from 0.001 to 5%, preferably from 0.01 to 1% byweight of a commercial enzyme preparation.

Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition. Higher active levels may be desirablein highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins that are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillis, having maximumactivity throughout the pH-range of 8-12, developed and sold asESPERASE® by Novozymes of Industries A/S of Denmark.

Other suitable proteases include ALCALASE®, EVERLASE®, LIQUANASE®, andSAVINASE®, and POLARZYME® from Novozymes, from PURAFECT®, andPROPERASE®, from Genencor International and MAXATASE® from InternationalBio-Synthetics, Inc., The Netherlands.

Suitable lipase enzymes for use in the composition of the inventioninclude those produced by microorganisms of the Pseudomonas group, suchas Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-1,372,034. Avery suitable lipase enzyme is the lipase derived from humicolalanuginosa and available from Novozymes, Denmark Nordisk under thetradename LIPOLASE®. Other suitable lipase enzames are LIPEX® fromNovozymes.

Suitable cellulose enzymes for use in the composition of the inventioninclude those produced by microorganism of the Aspergillus sp. Suitablecellulose enzymes are available under tradename CAREZYME®, CELLUZYME®,from Novozymes, PURADAX®, AND PRIMAFAST®LUNA from GenencorInternational.

Alpha-amylase enzymes can be produced by microorganism of Bacillus sp.and are available under the tradename as TERMAMYL®, STAINZYME®,DURAMYL®, from Novozymes, Denmark. Alpha-amylase enzyme is available asPURASTAR® from Genencor International.

Mannanase enzymes are available under tradename MANNAWAY®, fromNovozymes, Denmark and PURABRITE® from Genencor International.

Mixtures or blends of enzymes for use in the compositions of theinvention are available under tradename as T-BLENDEVERLASE/DURAMYL/LIPEX®, T-BLEND SAVINASE/CAREZYME®, T-BLENDSAVINASE/LIPEX®, T-BLEND SAVINASE/LIPOLASE®, T-BLENDSAVINASE/STAINZYME®, T-BLEND SAVINASE/TERMAMYL®, T-BLENDSAVINASE/TERMAMYL/CELLUZYME®, from Novozymes, Denmark.

Other Optional Components

In addition to the anionic and nonionic surfactants described above, thesurfactant system of the invention may optionally contain a cationicsurfactant.

Furthermore, alkaline buffers may be added to the compositions of theinvention, including monethanolamine, triethanolamine, borax, and thelike.

As another optional ingredient, an organic solvent may suitably bepresent in the gel composition of the invention, preferably at aconcentration of up to 10% by weight.

There may also be included in the formulation, minor amounts of soilsuspending or anti-redeposition agents, e.g. polyvinyl alcohol, fattyamides, sodium carboxymethyl cellulose or hydroxy-propyl methylcellulose.

Optical brighteners for cotton, polyamide and polyester fabrics, andanti-foam agents such as silicone oils and silicone oil emulsions mayalso be used.

Other optional ingredients which may be added in minor amounts, are soilrelease polymers, dye transfer inhibitors, polymeric dispersing agents,suds suppressors, dyes, perfumes, colourants, filler salts, antifadingagents and mixtures thereof.

Liquid Hand Dishwashing Detergents

While the following listing of ingredients is particularly suited forliquid hand dishwashing detergents, it is clearly within the scope ofone having skill in the art to determine whether such ingredients may beuseful for other detergent applications.

The concentration of the polyethylene glycol in the instant compositionis 0.5 to 10 wt. %, more preferably 0.75 wt. % to 6 wt. %.

Anionic Surfactants

Anionic sulfonate surfactants suitable for use herein include the saltsof C.sub.5-C.sub.20 linear alkylbenzene sulfonates, alkyl estersulfonates, C.sub.6-C.sub.22 primary or secondary alkane sulfonates,C.sub.6-C.sub.24 olefin sulfonates, sulfonated polycarboxylic acids,alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleylglycerol sulfonates, and any mixtures thereof.

Anionic sulfate surfactants suitable for use in the compositions of theinvention include linear and branched primary and secondary alkylsulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, andalkyl phenol ethylene oxide ether sulfates.

Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps(“alkyl carboxyls”).

An example of a preferred anionic surfactant (sulfonates & sulfates)would be the sodium salt of secondary alkane sulfonate commerciallyavailable under the tradename of Hostapur.® SAS (Clariant Corporation,Charlotte, N.C.).

Sulfonates: linear alkylbenzene sulfonate (LAS), alpha-olefin sulfonate(AOS), paraffin sulfonate (PS).

Sulfates: sodium lauryl sulfate (SLS), sodium lauryl ethoxy sulfate(SLES).

Water

The final ingredient in the inventive compositions is water. Theproportion of water in the compositions generally is in the range of 35%to 85%, preferably 50% to 80% by weight of the usual composition.

Amine Oxide

Amine oxides useful in the present invention include long-chain alkylamine oxides, ie., those compounds having the formula:

R³(OR⁴)_(x)—(NO)—(R⁵)₂

wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropyl andalkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbonatoms, preferably 8 to 16 carbon atoms; R⁴ is an alkylene orhydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2carbon atoms, or mixtures thereof; x is from 0 to 3, preferably 0; andeach R⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3,preferably from 1 to 2 carbon atoms, or a polyethylene oxide groupcontaining from 1 to 3, preferably 1, ethylene oxide groups. The R⁵groups can be attached to each other, e.g., through an oxygen ornitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxyethyl amineoxides and alkyl amido propyl amine oxide. Examples of such materialsinclude dimethyloctylamine oxide, diethyldecylamine oxide,bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,dodecylamidopropyl dimethylamine oxide anddimethyl-2-hydroxyoctadecylamine oxide. Preferred are C₁₀-C₁₈ alkyldimethylamine oxide, and C₁₀-C₁₈ acylamido alkyl dimethylamine oxide.

Betaine

The betaines useful in the present invention are those compounds havingthe formula R(R¹)₂N⁺R²COO⁻ wherein R is a C₆-C₁₈ hydrocarbyl group,preferably C₁₀-C₁₆ alkyl group, each R¹ is typically C₁-C₃, alkyl,preferably methyl, and R² is a C₁-C₅ hydrocarbyl group, preferably aC₁-C₅ alkylene group, more preferably a C₁-C₂ alkylene group. Examplesof suitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂-C₁₄ acylamidopropylbetaine; C₁₂-C₁₈acylamidohexyldiethyl betaine; 4-[C₁₄-C₁₆acylmethylamidodiethylammonio]-1-carboxybutane; C₁₆-C₁₈acylamidodimethylbetaine; C₁₂-C₁₆ acylamidopentanediethyl-betai-ne;C₁₂-C₁₆ acylmethyl-amidodimethylbetaine, and coco amidopropyl betaine.Preferred betaines are C₁₂-C₁₈ dimethylamoniohexanoate and the C₁₀-C₁₈acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Alsoincluded are sulfobetaines (sultaines) of formula R(R₁)₂N+R₂SO₃—,wherein R is a C₆-C₁₈ Hydrocarbyl group, preferably a C₁₀-C₁₆ alkylgroup, more preferably a C₁₂-C₁₃ alkyl group; each R₁ is typically C₁-C₃alkyl, preferably methyl and R₂ is a C₁-C₆ hydrocarbyl group, preferablya C₁-C₃ alkylene or, preferably, hydroxyalkylene group. Examples ofsuitable sultaines are C₁₂-C₁₄ dihydroxyethylammonio propane sulfonate,and C₁₆-C₁₈ dimethylammonio hexane sulfonate, with C₁₂-C₁₄ amido propylammonio-2-hydroxypropyl sultaine being preferred.

Alkanolamide Compounds

The present formulation can include an alkanolamide compound such as analkyl monoalkanol amide, an alkyl dialkanol amide, and mixtures thereof.

The formulation of the present invention can include a hydrotropeselected from the group consisting of ethanol, isopropanol, sodiumxylene sulfonate, propylene glycol, sodium cumene sulfonate, urea,polyethylene glycol and mixtures thereof.

Solvents

The formulation of the present invention can include a solvent selectedfrom the group consisting of alcohols (ethanol, isopropanol) glycols(propylene glycol, polyethylene glycol) polyols and polyethers(dipropylene glycol, dipropylene glycol methyl ether) and mixturesthereof. A variety of other water-miscible liquids such as loweralkanols, diols, other polyols, ethers, amines, and the like may be usedin the present invention. Preferred are the C₁-C₄ alkanols. When presentthe composition will preferably contain at least about 0.01%, morepreferably at least about 0.5%, even more preferably still, at leastabout 1% by weight of the composition of solvent. The composition willalso preferably contain no more than about 20%, more preferably no morethan about 10%, even more preferably, no more than about 8% by weight ofthe composition of solvent.

Inorganic Salt

The formulation of the present invention can include an inorganic ororganic salt or oxide of a multivalent cation, particularly Mg.sup.++which has phase stabilization properties. The multivalent cation salt oroxide provides several benefits including improved cleaning performancein dilute usage, particularly in soft water areas, and minimized amountsof perfume required to obtain the microemulsion state. Magnesiumsulfate, either anhydrous or hydrated (e.g., heptahydrate), is preferredas the magnesium salt. Good results also have been reported withmagnesium oxide, magnesium chloride, magnesium acetate, magnesiumpropionate and magnesium hydroxide. These magnesium salts can be usedwith formulations at neutral or acidic pH since magnesium hydroxide willnot precipitate at these pH levels.

Although magnesium is a preferred multivalent cation from which thesalts (inclusive of the oxide and hydroxide) are formed, otherpolyvalent metal ions also can be used provided that their salts arenontoxic and are soluble in the aqueous phase of the system at thedesired pH level.

Other Components

The liquid cleaning composition of this invention may, if desired, alsocontain other optional components either to provide additional effect orto make the product more attractive to the consumer. The following arementioned by way of example: Colorants or dyes in amounts up to 0.5% byweight; preservatives or antioxidizing agents, such as formalin,5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one,2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pHadjusting agents, such as sulfuric acid or sodium hydroxide, as needed.Furthermore, if opaque compositions are desired, up to 4% by weight ofan opacifier may be added. Preferably, the optional ingredients areselected from the group consisting of hydrotropes, perfumes, colorants,pH adjusting agents, preservatives, biocidal agents, inorganic salts,opacifiers, viscosity modifiers, and mixtures thereof.

Specialty Household Cleansers (SHC)

Specialty household cleaners of the invention comprise Bio-PDO and oneor more of the typical detergent ingredients set forth in the abovesections. Those having skill in the art can readily determineappropriate ingredients to combine with the Bio-PDO in order to obtain adesired specialty household cleaner.

Viscosity

Some detergent compositions containing Bio-PDO may require approximately30% less salt to adjust the viscosity than other compositions containingcomparable glycols such as propylene glycol, butylene glycol,2-methyl-1,3 propanediol etc. In other compositions, Bio-PDO may helpmaintain and build viscosity.

Heat Transfer Compositions

The term “heat transfer fluid” as used herein refers to a fluid orliquid that is capable of transferring and/or dissipating a quantity ofthermal energy from a first point to second point. Heat transfer fluidsinclude coolants.

Heat transfer fluid as used herein may include both concentratedsolutions of Bio-PDO mixtures as well as to diluted solutions of thesame mixed with water, preferably deionized water. It will beappreciated that although heat transfer fluid may be purchased,transported or used in concentrated solutions, such concentrates willoften be diluted with water, especially deionized water, prior toincorporation or use in, for example, a fuel cell. Exemplary heattransfer composition include, but are not limited to, heating medium forradiant heating systems and industrial heating applications, andHeating, Ventilation, and Air Conditioning applications, and thermalenergy storage, heating and cooling. Heat transfer fluids can also beused in a variety of markets, including vehicles and equipment (asantifreeze), process manufacturing industries (e.g., chemicals,pharmaceuticals, plastics, fiber and food), energy production, asphalt,laundry, biotechnology, cryogenic preservation, metalworking, mining,ice rinks, refrigeration systems and heating systems, metalworking,transportation, mining and others such as ice rinks.

In heat transfer compositions, the glycol is typically the majorcomponent of the composition, present in a range of from about 1% toabout 100%.

In antifreeze compositions, the glycol is typically the major componentof the composition, present in a range of from about 1% to about 100%.

In the heat transfer and antifreeze compositions of the invention, theBio-PDO can be the major component of the composition, present inamounts up to 100% by weight based on the weight of the totalcomposition. The amount of Bio-PDO used in the products is generally thebalance after adding the percentages of typical ingredients such ascorrosion inhibitors, foam suppressants, dyes and water,

Those of ordinary skill in the art will now understand that, underappropriate circumstances, considering issues such as corrosion,toxicity, viscosity, fluid life, equipment specifications, fluid color,cost, etc., other elements, such as for example, one or more of acolorant, a wetting agent, an antifoam agent, a biocide, a bitterant, anonionic dispersant, anti-foam agents, anti-icing additives, anti-wearadditives, demulsifiers, detergents, dispersants, emulsifiers, EPadditives, oiliness agents, oxidation inhibitors, pour pointdepressants, rust inhibitors, tackiness agents, viscosity improvers,preservatives, alcohols, or combinations thereof, and any other optionalingredients, may be added to the heat-transfer or antifreeze compositionof the invention.

More particularly, in addition to the Bio-PDO or otherbiologically-derived glycol component, a typical heat transfer fluidformulation of the invention may include one or more of water from1.0-95.0% by weight, corrosion inhibitors from 0.10% to 50.0%, foamsuppressors from 0.10% to 50.0%, and/or dyes from 0.10% to 50.0%.

In a typical antifreeze fluid or coolant formulation of the invention,in addition to the Bio-PDO or other biologically-derived glycolcomponent, such formulations may also include one or more of water from1.0-90.0% by weight, corrosion inhibitors from 0.10% to 50.0%, foamsuppressors from 0.10% to 50.0%, and dyes from 0.10% to 50.0%.

Ingredients

Set forth below is a non-limiting listing of ingredients that may beused in combination with Bio-PDO in heat transfer and antifreezeformulations of the present invention. This listing is not intended tobe all-inclusive, and those having skill in the art are familiar withother known ingredients that may apply to formulations of the invention.

Corrosion Inhibitors

Useful corrosion inhibitors can be used in an amount sufficient toinhibit or reduce corrosion of exposed metal surfaces in contact withthe engine cooling composition of the present invention, preferably inan amount of from 0.01 to 50% by weight. Preferable corrosion inhibitorsinclude any conventionally or commercially used corrosion inhibitor,including, but not limited to, inorganic nitrates and nitrates,preferably selected from the Na, K, Mg, Ca, and Li salts; azolesselected from tolyltriazole, hydrocarbyl triazole, benzotriazole,mercaptobenzothiazole, pyrazoles, isooxazoles, isothiazoles, thiazoles,thiadiazole salts, 1,2,3-benzotriazole, 1,2,3-tolyltriazole, and Na2-mercaptobenzothiazole; inorganic molybdates such as Na molybdate, Kmolybdate, Li molybdate, ammonium molybdate, ammonium dimolybdate, MoO3,heteropolymolybdates, disodium molybdate dihydrate,silicoheteropolymolybdates, and phosphoheteropolymolybdates;monocarboxylic acids, typically C₃₋₁₆-carboxylic (or fatty) acids (orthe corresponding alkali metal salts), esp. hexanoic, heptanoic,isoheptanoic, octanoic, 2-ethylhexanoic, nonanoic, decanoic, undecanoic,dodecanoic, and neodecanoic acids; inorganic phosphates include K2HPO4,Na2HPO4, KH2PO4, K3PO4, NaH2PO4, and Na3PO4 and mixtures thereof, forexample. More preferably the corrosion inhibitor is one of the PENRAYcorrosion inhibitors available from The Penray Companies, such as PENRAY2792 (an aqueous solution of nitrites, nitrates and sodium hydroxide).

Defoamers

Defoamers are used in an amount sufficient to reduce buildup of foam orreduce foam or trapped air by causing the bubbles to burst, thusreleasing the trapped air. Preferably a defoamer is used in an amount offrom 0.01 to 50% by weight. One or more than one defoamer may bepresent. Preferable defoamers include, but are not limited to, PATCOTE415 or 462 (an ethylene glycol n-butyl ether based defoamer made byAmerican Ingredients Company), PLURONIC L61 (a block copolymermanufactured by BASF Corp.), DOW AF9020 (a silicone emulsion produced byDow Chemical), ADVANTAGE 831 (a hydrocarbon oil emulsion produced byHercules, Inc.), POLYTERGENT P32A (an EO/PO copolymer made by OlinCorp.), LANDA 5600 (oil soluble, water miscible defoamer produced byLanda Corp.) and AF-20F (a silicone oil emulsion produced by PerformanceChemicals LLC), for example.

Water

The water contained in the composition can be any desired amount,preferably from 1 to 99% by weight. More preferably, the amount of wateris in the range from 30 to 70% by weight, most preferably from 40 to 60%by weight. The water is preferably distilled and/or deionized.Preferably, the water is deionized before contacting with the othercomponents of the composition.

Colorant/Dye

The present invention composition can contain a colorant/dye in order tohelp a user readily distinguish the composition from colorless liquids,particularly from water. Suitable colorants can be any conventionalcolorant, and can be any desired color, including but not limited toorange, blue, green, red and yellow, and any combination thereof. Ifpresent, the dye can be used in any amount to provide the color desired,preferably from 0.01 to 50% by weight. One or more than one dye may bepresent. More preferably, any light stable, transparent water solubleorganic dye is suitable, including but not limited to, Acid Red dyes,methylene blue, uranine dye, wool yellow dye and rhodamine dye, withdyes such as 15189 EOSINE OJ (an Acid Red 87 based dye commerciallyavailable from Chemcentral Dyes and Pigments) being particularlypreferred.

Fluorosurfactant

The composition of the present invention further comprises at least onefluorosurfactant in an amount of 0.001 to 50% by weight. Thefluorosurfactant desirably causes a reduction in contact angle (e.g.,droplet height) compared to an untreated water/glycol mixture, modifiesthe surface properties of liquids or solids, or reduces surface tensionin a fluid or the interfacial tension between two immiscible fluids, forexample oil and water. The measurement of contact angle and/or surfacetension is known in the art. The terms, fluorosurfactant and fluorinatedsurfactant are used interchangeably herein. Preferably, thefluorosurfactant is soluble in water. Preferable fluorosurfactantsinclude, but are not limited to, the ZONYL fluorosurfactants (anionic,nonionic and amphoteric fluorinated surfactants) including, but notlimited to, ZONYL FSA, FSE, FSJ, FSP, TBS, FSO, FSH, FSN, FSD and FSK,more preferably the non-ionic ZONYL fluorosurfactants, most preferablyZONYL FSH, FSN or FSP (typically mixtures of a fluoroalkyl alcoholsubstituted polyethylene glycol with water and a glycol or glycol ethersuch as dipropylene glycol methyl ether) (all commercially availablefrom DuPont). The fluorosurfactant can be used alone, or can be combinedwith other fluorosurfactants or non-fluorine containing surfactants asdesired.

Esters

Esters can function as many of the above noted ingredients. While thosein those having skill in the art can readily determine which esters aremost appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

Additional Ingredients

The present composition may optionally include one or more otheradditives. These include, but are not limited to, for example, alkalimetal borates as corrosion-inhibitors such as disclosed in U.S. Pat.Nos. 4,149,985, 2,566,923, 3,960,740, 2,373,570, and 2,815,328; alkalimetal sebacates as corrosion inhibitors such as disclosed in U.S. Pat.No. 2,726,215, U.K. Patent 1,004,259, U.S. Pat. Nos. 4,382,008,4,561,990, 4,587,028, and 4,588,513; alkali metal molybdates ascorrosion-inhibitors such as disclosed in U.S. Pat. Nos. 2,147,409 and4,561,990; alkali metal mercaptobenzothiazole such as disclosed in U.S.Pat. Nos. 2,815,328, 4,455,248, 4,414,126, and 4,545,925; alkali metalnitrates as corrosion-inhibitors such as disclosed in U.S. Pat. Nos.2,815,328, 4,508,684, 4,455,248, and 4,587,028; tolyltriazole such asdisclosed in U.S. Pat. Nos. 4,242,214, 2,587,028, 4,382,008, and U.K.Patent 1,004,259; alkali metal silicates such as disclosed in U.S. Pat.Nos. 2,815,328, 4,242,214, 4,382,008, 4,382,870, 4,455,248, and4,149,985, the relevant portions of each of which are herebyincorporated by reference.

Natural Ingredients

The heat transfer or antifreeze compositions of the invention cancontain any natural ingredients where appropriate. Natural ingredientsinclude any natural or nature-derived ingredients similar in compositionor in function to any of the ingredients listed above.

Deicing Compositions

The deicing/anti-icing compositions can be used in any applicationrequiring deicing and/or anti-icing. In some embodiments, thecompositions are used for the removal of, and/or time-limited protectionagainst, deposits of frost, ice, and/or snow on exterior aircraftsurfaces prior to take off, or on roadway/runway surfaces. Thecompositions can be applied through a commercial deicing/anti-icingvehicle system to the surfaces at pressures and flow rates normal forintended use.

In addition to application to aircraft, the compositions can also beused for other anti-icing/deicing applications, such as, surfaces of,for example, airport pavements, roadways, walkways, sidewalks, bridges,entrances, electrical tower structures and their components, electricitytransmission lines, canals, locks, vessels, nautical components,railroad switches, and motor vehicles. In addition, the compositions canbe used in applications such as birdbaths, outdoor fountains, decorativeponds, and other outdoor areas where water freezing would beaesthetically or functionally unacceptable. In these applications thefluids can prevent water from freezing during the winter in coldclimates with reduced biological risk to wildlife or domestic animals.

It is also envisioned that the compositions of the present invention canbe used in either a liquid or a solid format. For instance, the compoundcan be prepared as a liquid and sprayed on or spread on surfaces.Alternatively, it can be prepared in a solid form and employed as apowder. Optionally, the solid may be further processed using methodswell known in the art, such as, for example, pelletizing, prilling,flaking, or macerating to provide the formulation in a final useablepowdered or granular form. Any of the binders known to those skilled inthe art optionally may be present and may either be inert or may becomprised of components that actively help lower the freezing point. Forexample, cinders, sawdust, sand, gravel, sugars, maltodextrins andmixtures thereof and the like can be used.

In the methods of the present invention, the deicing and/or anti-icingcompositions of the present invention are applied, such as by sprayingor injecting for liquid forms.

In the anti-icing or deicing compositions of the invention, the Bio-PDOor other bio-derived glycol component can be the major component of thecomposition, present in amounts up to 100% by weight based on the weightof the total composition. The amount of Bio-PDO used in the products isgenerally the balance after adding one or more of surfactant, corrosioninhibitors, water, and any optional ingredients. Deicing/anti-icingfluids preferably contain from about 10% to about 95% Bio-PDO by weight,and more preferably from about 25% to about 92%. A typical formulationfor aircraft deicing/anti-icing may include, but is not limited to, thefollowing components: 25-95% by weight of Bio-PDO or mixture thereof;and up to 1% each of the following components: at least one surfactantor surfactant blend, at least one corrosion inhibitor, a pH controlagent, a thickening agent, and a dye. Water can make up the balance ofthis formulation. Further details on alternative formulations andingredients is provided below.

In certain embodiments, such as those containing glycerol in combinationwith Bio-PDO, the compositions of the invention preferably contain fromabout 10% to about 88% glycerol and as such, from as little as about 1%to about 30% Bio-PDO.

Functional and Other Ingredients

The deicing/anti-icing products of the invention can include one or morefunctional and other ingredients. Functional and other ingredientsuseful herein may be categorized or described herein by their benefit ortheir postulated mode of action in the deicing or anti-icingcomposition. However, it is to be understood that the functional andother ingredients useful herein can in some instances provide more thanone benefit or operate via more than one mode of action. Therefore,classifications herein are made for the sake of convenience and are notintended to limit an ingredient to the particularly stated applicationor applications listed.

Surfactants

A preferred surfactant is a nonionic surfactant; anionic, cationic, andamphoteric (zwitterionic) surfactants are less preferred. Somenonlimiting examples of suitable nonionic surfactants are: alkylphenolethoxylates (C₁₂ or lower, C₈ or lower preferred); fatty or oxo-alcoholpolyethyleneglycol ethers (C₁₆ or lower, C₆ or lower preferred);ethylene oxide-propylene oxide polymers (C₈₀ or lower, C₂ or lowerpreferred); fatty alcohol polyglycol ethers (C₁₈ or lower, C₈ or lowerpreferred); polyethoxylates such as polyoxyethylene ethers;polypropyloxylates such as polyoxypropylene ethers; sugar-basedsurfactants such as alkyl glycosides (e.g., alkyl benzene andtert-butoxyethanol); ethers of C₁ to C₈ polyethylene oxide repeat unitsof 2 to 50 polyethylene oxide units (low carbon alkyl group and somewhathigher carbon ethoxylate group preferred); polyvinyl alcohols having MW1000-10,000; and polyvinyl pyrrolidones.

The nonionic surfactants can be selected from polyoxyalkylene ethers.Some preferred polyoxyalkylene ethers are ethers of C₁₂ to C₁₈ alcoholswith polyethylene oxide repeat units of 2 to 100 polyethylene oxideunits. Such surfactants include, for example, the Brij™ series ofsurfactants manufactured by ICI (e.g., Brij 30, 35, 52, 56, 58, 72, 76,78, 92, 97, 98 and 700). Brij 35 is polyoxyethylene lauryl ether, 718average MW, having the chemical formula: CH₃(CH₂)₁₁(CH₂CH₂₀)_(xH), wherex on average is 23.

The fluids can contain any suitable amount of surfactant. Preferably,the fluids contain from about 0.01% to about 0.9% surfactant by weight,and more preferably from about 0.05% to about 0.5%.

pH Control Agent

The deicing/anti-icing compositions of the invention can optionallyinclude one or more pH control agents to maintain the fluid at constantpH. The compositions can have any suitable pH. The pH of thecompositions can range anywhere from about 3.5 to about 12, andpreferably from about 6 to about 9. The desired pH can be obtained usinginorganic bases such as sodium hydroxide, ammonium hydroxide andpotassium hydroxide, or amines such as triethanol amine, diethanol amineor monoethanol amine.

Some nonlimiting examples of suitable buffers include: phosphate salts(K⁺, NH₄ ⁺); pyrophosphates (Na⁺, K⁺, NH₄ ⁺); metaphosphates (Na⁺, K⁺,NH₄ ⁺); carbonic acid and its salts (Na⁺, K⁺, NH₄ ⁺); hydroxylammonium(Na⁺, K⁺, NH₄ ⁺); adidic acid and its salts (Na⁺, K⁺, NH₄ ⁺); maleicacid and its salts (Na⁺, K⁺, NH₄ ⁺); and ascorbic acid and its salts(Na⁺, K⁺, NH₄ ⁺).

Defoamers

Defoamers may also be employed. Any commercially available defoamer orantifoamer can be used, but particularly preferred defoamers are asilicone defoamer of Union Carbide Corporation sold under the trademarkSAG, and FOAMBAN™ defoamer available from Ultra Additives Inc.,Patterson, N.J. The amount of defoamer to be used is preferably in therange of from about 0.05% to about 0.5% by weight based on the weight ofthe total composition.

Corrosion Inhibitors

Suitable corrosion inhibitors are known to the art, and typicallycomprise mixtures of various functional materials, e.g., buffers,chelating agents, and the like, esters of inorganic acids such as thephosphorus and boron, aromatic triazoles such as tolyl- andbenzyltriazole, and the like, in one or more solvents. A preferredanticorrosion mixture is that product sold by Sandoz under thedesignation “Sandocorin 8132”. Those having skill in the art understandthat selection of appropriate corrosion inhibitor may be made based uponthe type of surfaces which the present compositions are likely to comein contact with, and how long and under what conditions they are likelyto remain on that surface.

Suitable corrosion inhibitors include those belonging to the groupcomprising inorganic metal salts, alkali metal salts of fatty acids,monoalkyl amines and dialkyl amines optionally alkoxylated—and saltsthereof, alkanol amines—optionally alkoxylated and salts thereof, estersof phosphorus acid or of phosphoric acid, and triazoles. The amount ofcorrosion inhibitor to be used is preferably in the range of from about0.05% to about 0.8% by weight based on the weight of the totalcomposition.

Thickening Agents

Thickening agents can be used in the compositions of the invention, andoften comprise polymeric water-activated thickening agents. Thickeningagents will typically comprise between 0.1 and 15.0 weight percent ofthe total composition. Examples include polysaccharide thickeners,natural gum thickeners, marine algae colloids, and cellulose etherthickeners. A preferred thickener is a polysaccharide known genericallyas Xanthan Gum.

Oils

The composition can optionally contain at least one non-polar oil, suchas aliphatic and aromatic oils such as mineral oil, paraffin oil,silicone oil, and propylene oxide/ethylene oxide copolymers. The amountof such oils is frequently in the range of from about 0.01% to about 5%by weight based on the total weight of the composition. The preferredrange is between 0.1% to 1.0% by weight based on the total weight of thecomposition.

Thermal Stabilizing Agents

The deicing/anti-icing products can further include a material thatimproves the thermal stability of the material. Any suitable materialhaving these properties can be used, for example certain of thephosphate salts. A particular example is a mixture of mono-basic sodiumphosphate and di-basic sodium phosphate, such as the monohydratemono-basic and heptahydrate di-basic sodium phosphates.

The products can contain any suitable amount of the buffer/freezingpoint depressant. The fluids preferably contain from about 0.02% toabout 2% mono-basic sodium phosphate and from about 0.02% to about 2%di-basic sodium phosphate by weight, more preferably from about 0.3% toabout 1.5% mono-basic sodium phosphate and from about 0.3% to about 1.5%di-basic sodium phosphate.

Anti-Microbial Agents

The deicing/anti-icing products can optionally include one or moreanti-microbial agents. Some nonlimiting examples of suitableanti-microbial agents include: sodium azide; quaternary ammoniumcompounds (e.g., 2-methyl-4,5-trimethylene-4-isothizoline-3-one; n-alkyldimethyl benzyl ammonium X⁻ [where alkyl carbon number is C₁₂₋₁₈];n-alkyl trimethyl ammonium X⁻ [where alkyl carbon number is C₁₂₋₁₈];dialkyl dimethyl ammonium X″ [where alkyl carbon number is C₁₂₋₁₈];octyl decyl dimethyl ammonium X⁻ [where X⁻ is Br, I₃ ⁻, HCO₃ ⁻, CO₃ ²⁻,phosphates, phosphonates, OH, carboxylates, polycarboxylates]);benzoates (where M⁺ is Na⁺, K⁺, NH₄ ⁺; alkyl dimethyl benzyl ammoniumchlorides; and alkyl dimethyl benzyl/ethyl benzyl ammonium chlorides.

Fire Retardants

The deicing/anti-icing products can also optionally include one or moreflame and/or corrosion inhibitors. Some common additives used for bothfire and corrosion inhibition include sodium tolyltriazole and1H-benzotriazole, methyl.

Vinylpyrrolidone

In another embodiment of the invention, the deicing/anti-icing fluidsinclude a biobased freezing point depressant as described above, incombination with a vinylpyrrolidone polymer having a molecular weightbetween about 10,000 and about 700,000, and water. By “vinylpyrrolidonepolymer” is meant a homopolymer or a copolymer of vinylpyrrolidone, or aderivative thereof. Suitable derivatives of vinylpyrrolidine polymer mayinclude alkylated polyvinylpyrrolidones, 2-menthyl. Preferably, thevinylpyrrolidone polymer is polyvinylpyrrolidone.

The vinylpyrrolidone polymer preferably has a molecular weight betweenabout 10,000 and about 700,000, and preferably not greater than about360,000. It is believed that higher molecular weight vinylpyrrolidonepolymers may produce deicing/anti-icing fluids having less desirableproperties, particularly for aircraft and runway deicing.

The deicing/anti-icing products can contain any suitable amount of thevinylpyrrolidone polymer. Typically, the products contain about 5% orless vinylpyrrolidone polymer, and usually between about 0.1% and about3%.

Advantageously, the vinylpyrrolidone polymer often functions as both athickener and a surfactant in the fluid. Consequently, products havingdesirable properties can be produced using a minimal number ofingredients. However, optionally the products can also contain otheringredients such as an antioxidant and/or a second surfactant.

Aqueous Solvents

The deicing/anti-icing products can also include an aqueous solvent(i.e. water) in any suitable amount, usually in an amount of from about30% to about 70% by weight. It should be noted that the percentages ofingredients given herein are based on a ready-to-use products. Theproducts of the invention can also be provided in a concentrateformulation, in which case the percentage of aqueous solvent willdecrease (e.g., the concentrate may contain from about 5% to about 20%water) and the percentages of other materials will increase accordingly.

Colorants or Dyes

The deicing/anti-icing products can also include an colorants or dyes inany suitable amount, usually in an amount up to 0.25% by volume of theformulation.

Esters

Esters can function as many of the above noted ingredients. While thosein those having skill in the art can readily determine which esters aremost appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

Miscellaneous Additives

The composition may also contain various other functional ingredientssuch as UV inhibitors, odor-modification agents, stabilizers and thelike. Each of these components will typically comprise less than 1.0weight percent of the total composition.

In specific applications, certain embodiments of the present inventionare especially preferred due to certain regulatory or industryguidelines. For example, in the deicing and/or anti-icing of aircraft,it is preferred to use deicing and/or anti-icing fluids of Bio-PDO,water; a mixture of Bio-PDO and other bio-derived glycols and water, ora mixture of Bio-PDO, petrochemically derived glycols, and water. agentsof methyl glucoside; a mixture of sorbitol and Bio-PDO; or a mixture ofmethyl glucoside, sorbitol and Bio-PDO with sodium lactate and/orpotassium lactate.

For the deicing and/or anti-icing of runways, it may be preferable touse deicing and/or anti-icing agents of sodium lactate; potassiumlactate; a mixture of sodium lactate and potassium lactate; ahydroxyl-containing organic compound in combination with sodium lactate,potassium lactate and/or potassium acetate as well as Bio-PDO; a mixtureof sodium lactate and/or potassium lactate with potassium acetate; orpotassium carbonate and Bio-PDO.

For de-icing and/or anti-icing of pre-harvest fruits and vegetables,such as fruit trees or grape vines, it may be preferable to use de-icingand/or anti-icing agents of a hydroxyl-containing organic compound incombination with Bio-PDO and an organic acid salt, particularly alactate salt.\

The deicing and anti-icing compositions of the invention can contain anynatural ingredients where appropriate. Natural ingredients include anynatural or nature-derived ingredients similar in composition or infunction to any of the ingredients listed above.

Food Compositions

The food compositions of the invention include a food or food componentconsisting of one or more food ingredients. Further, a food compositionincludes human food, substances migrating to food from food-contactarticles, beverages, pet food, and animal feed compositions.

A “food ingredient” includes any ingredient that can be used in a foodcomposition. It is preferred that an ingredient be of appropriate foodgrade; that it be prepared and handled as a food ingredient; and thatthe quantity of the ingredient added to food does not exceed the amountreasonably required to accomplish the intended physical, nutritional, orother technical effect in food.

Food compositions of the invention can comprise from 0.1% to 100%Bio-PDO by weight, and more preferably from about 2% to about 97%Bio-PDO by weight. A typical food composition formulation of the presentinvention could include 2% to 97% Bio-PDO and 3% to 98% of one or moreingredients.

In the food compositions of the invention, the Bio-PDO can be ananticaking agent, free-flow agent, antioxidant, dough strengthener,emulsifier, emulsifier salt, flavoring agent, flavoring adjuvant,formulation aid, humectant, processing aid, solvent, vehicle,stabilizer, thickener, surface-active agent, and/or texturizer.

As they relate to the function of the Bio-PDO in the food compositionsof the invention, the following definitions are applicable.

“Anticaking agents and free-flow agents” are generally defined assubstances added to finely powdered or crystalline food products toprevent caking, lumping, or agglomeration.

“Antioxidants” are generally defined as substances used to preserve foodby retarding deterioration, rancidity, or discoloration due tooxidation.

“Dough strengtheners” are generally defined as substances used to modifystarch and gluten, thereby producing a more stable dough, including theapplicable effects listed by the National Academy of Sciences/NationalResearch Council under “dough conditioner.”

“Emulsifiers and emulsifier salts” are generally defined as substanceswhich modify surface tension in the component phase of an emulsion toestablish a uniform dispersion or emulsion.

“Flavoring agents and adjuvants” are generally defined as substancesadded to impart or help impart a taste or aroma in food.

“Formulation aids” are generally defined as substances used to promoteor produce a desired physical state or texture in food, includingcarriers, binders, fillers, plasticizers, film-formers, and tabletingaids, etc.

“Humectants” are generally defined as hygroscopic substancesincorporated in food to promote retention of moisture, includingmoisture-retention agents and antidusting agents.

“Processing aids” are generally defined as substances used asmanufacturing aids to enhance the appeal or utility of a food or foodcomponent, including clarifying agents, clouding agents, catalysts,flocculents, filter aids, and crystallization inhibitors, etc.

“Solvents and vehicles” are generally defined as substances used toextract or dissolve another substance.

“Stabilizers and thickeners” are generally defined as substances used toproduce viscous solutions or dispersions, to impart body, improveconsistency, or stabilize emulsions, including suspending and bodyingagents, setting agents, jellying agents, and bulking agents, etc.

“Surface-active agents” are generally defined as substances used tomodify surface properties of liquid food components for a variety ofeffects, other than emulsifiers, but including solubilizing agents,dispersants, detergents, wetting agents, rehydration enhancers, whippingagents, foaming agents, and defoaming agents, etc.

“Texturizers” are generally defined as substances which affect theappearance or feel of the food.

Food Ingredients

As described above, in a preferred embodiment, the food composition ofthe invention comprises the 1,3-propanediol of the invention and atleast one food ingredient. Below is a non-limiting description ofingredients that can be used in the food compositions of the invention.

The U.S. Food and Drug Administration (FDA) Center for Food Safety andApplied Nutrition (CFSAN) maintains a database (“EAFUS: A Food Additivedatabase”; http://vm.cfsan.fda.gov/˜dms/eafus.html) under an ongoingprogram known as the Priority-based Assessment of Food Additives (PAFA).PAFA contains administrative, chemical and toxicological information onover 2000 substances directly added to food, including substancesregulated by the U.S. FDA as direct, “secondary” direct, and coloradditives, and Generally Recognized As Safe (GRAS) and prior-sanctionedsubstances. In addition, the database contains only administrative andchemical information on less than 1000 such substances. The more than3000 total substances together comprise an inventory often referred toas “Everything” Added to Food in the United States (EAFUS). It iscontemplated that all ingredients listed in the EAFUS can be used asingredients in the food compositions of the invention, and those havingskill in the art can readily determine appropriate ingredients forparticular food products. The EAFUS Food Additive Database describedabove is herein incorporated by reference in its entirety.

The EAFUS list of substances contains ingredients added directly to foodthat FDA has either approved as food additives or listed or affirmed asGRAS. Nevertheless, it contains only a partial list of all foodingredients that may in fact be lawfully added to food, because underfederal law some ingredients may be added to food under a GRASdetermination made independently from the FDA. The list contains many,but not all, of the substances subject to independent GRASdeterminations. For information about the GRAS notification programplease consult the Inventory of GRAS Notifications. Additionalinformation on the status of Food and Color Additives can be obtainedfrom the Food Additive Status List or the Color Additive Status List(formerly called Appendix A of the Investigations Operations Manual).

The following summary is copied directly from the EAFUS Food d AdditiveDatabase and lists certain types of common food ingredients, why theyare used, and some examples of the names that can be found on productlabels. Some additives are used for more than one purpose.

The ingredient listings below are organized as follows:

Ingredient Category

-   -   Ingredient Function    -   Food Category    -   Ingredient Example

Preservatives

Prevent food spoilage from bacteria, molds, fungi, or yeast(antimicrobials); slow or prevent changes in color, flavor, or textureand delay rancidity (antioxidants); maintain freshness.

Fruit sauces and jellies, beverages, baked goods, cured meats, oils andmargarines, cereals, dressings, snack foods, fruits and vegetables

Ascorbic acid, citric acid, sodium benzoate, calcium propionate, sodiumerythorbate, sodium nitrite, calcium sorbate, potassium sorbate, BHA,BHT, EDTA, tocopherols (Vitamin E)

Sweeteners

Add sweetness with or without the extra calories

Beverages, baked goods, confections, table-top sugar, substitutes, manyprocessed foods

Sucrose (sugar), glucose, fructose, sorbitol, mannitol, corn syrup, highfructose corn syrup, saccharin, aspartame, sucralose, acesulfamepotassium (acesulfame-K), neotame

Color Additives

Offset color loss due to exposure to light, air, temperature extremes,moisture and storage conditions; correct natural variations in color;enhance colors that occur naturally; provide color to colorless and“fun” foods

Many processed foods, (candies, snack foods margarine, cheese, softdrinks, jams/jellies, gelatins, pudding and pie fillings) FD&C Blue Nos.1 and 2, FD&C Green No. 3, FD&C Red Nos. 3 and 40, FD&C Yellow Nos. 5and 6, Orange B, Citrus Red No. 2, annatto extract, beta-carotene, grapeskin extract, cochineal extract or carmine, paprika oleoresin, caramelcolor, fruit and vegetable juices, saffron (Note: Exempt color additivesare not required to be declared by name on labels but may be declaredsimply as colorings or color added)

Flavors and Spices

Add specific flavors (natural and synthetic)

Pudding and pie fillings, gelatin dessert mixes, cake mixes, saladdressings, candies, soft drinks, ice cream, BBQ sauce

Natural flavoring, artificial flavor, and spices

Flavor Enhancers

Enhance flavors already present in foods (without providing their ownseparate flavor)

Many processed foods

Monosodium glutamate (MSG), hydrolyzed soy protein, autolyzed yeastextract, disodium guanylate or inosinate

Fat Replacers (and Components of Formulations Used to Replace Fats)

Provide expected texture and a creamy “mouth-feel” in reduced-fat foods

Baked goods, dressings, frozen desserts, confections, cake and dessertmixes, dairy products

Olestra, cellulose gel, carrageenan, polydextrose, modified food starch,microparticulated egg white protein, guar gum, xanthan gum, whey proteinconcentrate

Nutrients

Replace vitamins and minerals lost in processing (enrichment), addnutrients that may be lacking in the diet (fortification)

Flour, breads, cereals, rice, macaroni, margarine, salt, milk, fruitbeverages, energy bars, instant breakfast drinks

Thiamine hydrochloride, riboflavin (Vitamin B2), niacin, niacinamide,folate or folic acid, beta carotene, potassium iodide, iron or ferroussulfate, alpha tocopherols, ascorbic acid, Vitamin D, amino acids(L-ryptophan, L-lysine, L-leucine, L-methionine)

Emulsifiers

Allow smooth mixing of ingredients, prevent separation. Keep emulsifiedproducts stable, reduce stickiness, control crystallization, keepingredients dispersed, and to help products dissolve more easily

Salad dressings, peanut butter, chocolate, margarine, frozen desserts

Soy lecithin, mono- and diglycerides, egg yolks, polysorbates, sorbitanmonostearate

Stabilizers and Thickeners, Binders, Texturizers

Produce uniform texture, improve “mouth-feel”

Frozen desserts, dairy products, cakes, pudding and gelatin mixes,dressings, jams and jellies, sauces

Gelatin, pectin, guar gum, carrageenan, xanthan gum, whey

pH Control Agents and Acidulants

Control acidity and alkalinity, prevent spoilage

Beverages, frozen desserts, chocolate, low acid canned foods, bakingpowder

Lactic acid, citric acid, ammonium hydroxide, sodium carbonate

Leavening Agents

Promote rising of baked goods

Breads and other baked goods

Baking soda, monocalcium phosphate, calcium carbonate

Anti-Caking Agents

Keep powdered foods free-flowing, prevent moisture absorption

Salt, baking powder, confectioner's sugar

Calcium silicate, iron ammonium citrate, silicon dioxide

Humectants

Retain moisture

Shredded coconut, marshmallows, soft candies, confections

Glycerin, sorbitol, Propylene Glycol

Yeast Nutrients

Promote growth of yeast

Breads and other baked goods

Calcium sulfate, ammonium phosphate

Dough Strengtheners and Conditioners

Produce more stable dough

Breads and other baked goods

Ammonium sulfate, azodicarbonamide, L-cysteine

Firming Agents

Maintain crispness and firmness

Processed fruits and vegetables

Calcium chloride, calcium lactate

Enzyme Preparations

Modify proteins, polysaccharides and fats

Cheese, dairy products, meat

Enzymes, lactase, papain, rennet, chymosin

Gases

Serve as propellant, aerate, or create carbonation

Oil cooking spray, whipped cream, carbonated beverages

Carbon dioxide, nitrous oxide

In addition, esters can function as many of the above noted ingredients.While those in those having skill in the art can readily determine whichesters are most appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

One aspect of the invention is a process for producing an ester, eitheror both a monoester and a diester, from biologically-produced1,3-propanediol. The process comprises (a) providing 1,3-propanediolproduced biologically through fermentation and catalytic conversion ofatmospheric carbon; (b) contacting said 1,3-propanediol with an organicacid wherein said ester is produced; and (c) recovering said ester.

Esters of bio-PDO can be synthesized by contacting bio-PDO with anorganic acid. The organic acid can be from any origin, preferably eithera biosource or synthesized from a fossil source. Most preferably theorganic acid is derived from natural sources or bio-derived havingformula R₁R₂—COOH. Wherein the substituent R₁ can be saturated orunsaturated, substituted or unsubstituted, aliphatic or aromatic, linearor branched hydrocarbon having chain length 1 to 40 or their salts oralkyl esters. Wherein the substituent R₂ can be H or COOH. Thehydrocarbon chain can also have one or more functional groups such asalkene, amide, amine, carbonyl, carboxylic acid, halide, and hydroxylgroups. Naturally occurring organic acids are preferred, especiallythose produced by a biological organism, these could be classified asbio-produced and the resulting ester or diester could thereby also beclassified as bio-produced. Naturally occurring sources of such fattyacids include coconut oil, various animal tallows, lanolin, fish oil,beeswax, palm oil, peanut oil, olive oil, cottonseed oil, soybean oil,corn oil, and rape seed oil. Conventional fractionation and/orhydrolysis techniques can be used if necessary to obtain the fatty acidsfrom such materials. The following acids and their salts or alkyl estersare specifically preferred, acetic, butyric, lauric, myristic, palmitic,stearic, arachidic, adipic, benzoic, caprylic, maleic, palmitic,phthalic, sebacic, archidonic, erucic, palmitoleic, pentadecanoic,heptadecanoic, nondecanoic, octadectetraenoic, eicosatetraenoic,eicosapentaenoic, docasapentaenoic, tetracosapentaenoic, tetrahexaenoic,docosahexenoic, (alpha)-linolenic, docosahexaenoic, eicosapentaenoic,linoleic, arachidonic, oleic, erucic, formic, propionic, valeric,caproic, capric, oxalic, malonic, succinic, glutaric, adipic, pimelic,suberic, azelaic, tartaric, citric, salicylic, acetyl-salicylic,terephthalic, isophthalic, pelargonic, behenic, cerotic, margaric,montanic, melissic, lacceroic, ceromelissic, geddic, ceroplasticundecylenic, ricinoleic, and elaeostearic acid as well as mixtures ofsuch acids. A more preferred list of suitable organic acids are acetic,adipic, benzoic, maleic, sebacic, oxalic and mixtures of such acids. Amore preferred list of suitable “fatty acids” meaning generally acidsnamed containing 8-40 carbon in the carbon useful in the presentinvention include butyric, valeric, caproic, caprylic, pelargonic,capric, lauric, myristic, palmitic, stearic, arachidic, behenic,cerotic, oleic, linoleic, linolenic, margaric, montanic, melissic,lacceroic, ceromelissic, geddic, ceroplastic and the mixtures of suchacids. Among those acids, these acids, and their salts and alkyl estersare most preferred stearic, lauric, palmetic, oleic, 2-ethyl hexanoic,and 12-hydroxystearic and mixtures of such acids.

Generally 1,3-propanediol can be contacted, preferably in the presenceof an inert gas reacted with a fatty acid or mixture of fatty acids orsalts of fatty acids in the absence or presence of a catalyst or mixtureof two or more catalysts, at temperatures ranging from 25° C. to 400° C.

During the contacting, water is formed and can be removed in the inertgas stream or under vacuum to drive the reaction complete. Any volatilebyproducts can be removed similarly. When the reaction is complete, theheating can be stopped and cooled.

The catalyst can be removed preferably by dissolving and removing indeionized water. If catalyst can be removed by treating with deionizedwater, the reaction mixture is treated with aqueous solutions of acid orbase to forms salts and removing the salts either by washing orfiltering.

Further purification to obtain high purity fatty esters, preferably forpharmaceutical application can be carried out by dissolving in a solventthat dissolves fatty ester easily at higher temperatures and least atlower temperatures and recrystallizing with or without addition ofadditional solvent at low temperatures.

The catalyst can be an acid for non-limiting examples, sulfuric acid, orp-toluene sulfonic acid. The catalyst can also be a base, fornon-limiting example, sodium hydroxide. The catalyst can also be a salt,for non-limiting example, potassium acetate. The catalyst can also be analkoxide, for non-limiting example, titanium tetraisopropoxide. Thecatalyst can also be a heterogeneous catalyst, for non-limitingexamples: zeolite, heteropolyacid, amberlyst, or ion exchange resin. Thecatalyst can also be a metal salt, for non-limiting examples, tinchloride, or copper chloride. The catalyst can also be an enzyme, suchas those known in the art. The catalyst can also be an organic acid, fora non-limiting example, formic acid. Finally the catalyst can also be anorganometalic compound, for a non-limiting example, n-butylstannoicacid.

This process can be carried out in the presence or absence of a solvent.If a solvent is not necessary to facilitate the production of fattyester, it is preferred that the process is carried out in the absence ofsolvent.

The process can be carried out at atmospheric pressure or under vacuumor under pressurized conditions.

Where R₁ and R₂ is a hydrocarbon, preferably with a carbon chain lengthof about 1 to about 40. Such hydrocarbons can be saturated orunsaturated, substituted or unsubstituted, linear or branched;

M is hydrogen, an alkali metal or an alkyl group.

Where R₁ is a hydrocarbon, preferably with a carbon chain length ofabout 1 to about 40. Such hydrocarbons can be saturated or unsaturated,substituted or unsubstituted, linear or branched;

M is hydrogen, an alkali metal or an alkyl group.

Any molar ratio of diol to dicarboxylic acid or its salt or its estercan be used. The preferred range of the diol to dicarboxylic acid isfrom about 1:3 to about 2:1. This ratio can be adjusted to shift thefavor of the reaction from monoester production to diester production.Generally, to favor the production of diesters slightly more than abouta 1:2 ratio is used; whereas to favor the production of monoesters abouta 1:1 ratio is used. In general, if the diester product is desired overthe monoester the ratio of diol to dicarboxylic acid can range fromabout 1.01:2 to about 1.1:2; however if the monoester is desired a rangeof ratios from about 1.01:1 to about 2:1 is used.

The catalyst content for the reaction can be from 1 ppm to 60 wt % ofthe reaction mixture, preferably from 10 ppm to 10 wt %, more preferablyfrom 50 ppm to 2 wt % of the reaction mixture.

The product may contain diesters, monoesters or combination diesters andmonoesters and small percentage of unreacted acid and diol depending onthe reaction conditions. Unreacted diol can be removed by washing withdeionized water. Unreacted acid can be removed by washing with deionizedwater or aqueous solutions having base or during recrystallization.

Any ester of 1,3-propandiol can be made using the present invention. Thepreferred use of the invention is to produce short, middle and longchain monoesters and diesters of the 1,3-propanediol can be made withthe present invention, specifically this means those acids containingbetween about 1 and about 36 carbons in the alkyl chain. The followingis a list of most preferred monoesters and diesters that can be producedwith the present invention include propanediol distearate (monostearateand the mixture), propandiol dilaurate (monolaurate and the mixture),propanediol dioleate (monooleate and the mixture), propanedioldivalerate (monovalerate and the mixture), propanediol dicaprylate(monocaprylate and the mixture), propanediol dimyristate (monomyristateand the mixture), propanediol dipalmitate (monopalmitate and themixture), propanediol dibehenate (monobehenate and the mixture),propanediol diadipate, propanediol dimaleate, propanediol dioxalate,propanediol dibenzoate, and propanediol diacetate. These products canhave a wide range of application, but the preferred use of the abovelisted esters are as additives in cosmetic and liquid detergentapplications.

The food compositions of the invention can contain any naturalingredients where appropriate. Natural ingredients include any naturalor nature-derived ingredients similar in composition or in function toany of the ingredients listed above.

Food and Beverage Applications

Below is a non-limiting listing of food compositions of the inventioncomprising the 1,3-propanediol of the invention:

Herbs, seeds, spices, seasonings, blends, extracts, and flavorings,including all natural and artificial spices, blends, and flavors,containing up to about 97% by weight Bio-PDO by weight.

Confections and frostings, including candy and flavored frostings,marshmallows, baking chocolate, and brown, lump, rock, maple, powdered,and raw sugars containing up to about 24% Bio-PDO by weight.

Alcoholic beverages, including malt beverages, wines, distilled liquors,and cocktail mix containing up to about 5% Bio-PDO by weight.

Nuts and nut products, including whole or shelled tree nuts, peanuts,coconut, and nut and peanut spreads, containing up to about 5% Bio-PDOby weight.

Frozen dairy desserts and mixes, including ice cream, ice milks,sherbets, and other frozen dairy desserts and specialties, containing upto about 2.5% Bio-PDO by weight.

Baked goods and baking mixes, including all ready-to-eat andready-to-bake products, flours, and mixes requiring preparation beforeserving, containing up to about 2% bio-PDO by weight.

Nonalcoholic beverages and beverage bases, including only special orspiced teas, soft drinks, coffee substitutes, and fruit and vegetableflavored gelatin drinks, containing up to about 2% Bio-PDO by weight.

Breakfast cereals, including ready-to-eat and instant and regular hotcereals, containing up to about 2% Bio-PDO by weight.

Cheeses, including curd and whey cheeses, cream, natural, grating,processed, spread, dip, and miscellaneous cheeses, containing up toabout 2% Bio-PDO by weight.

Chewing gum, including all forms, containing up to about 2% Bio-PDO byweight.

Coffee and tea, including regular, decaffeinated, and instant types,containing up to about 2% Bio-PDO by weight.

Condiments and relishes, including plain seasoning sauces and spreads,olives, pickles, and relishes, but not spices or herbs, containing up toabout 2% Bio-PDO by weight.

Dairy product analogs, including nondairy milk, frozen or liquidcreamers, coffee whiteners, toppings, and other nondairy products,containing up to about 2% Bio-PDO by weight.

Egg products, including liquid, frozen, or dried eggs, and egg dishesmade therefrom, i.e., egg roll, egg foo young, egg salad, and frozenmulticourse egg meals, but not fresh eggs, containing up to about 2%Bio-PDO by weight.

Fats and oils, including margarine, dressings for salads, butter, saladoils, shortenings and cooking oils, containing up to about 2% Bio-PDO byweight.

Fish products, including all prepared main dishes, salads, appetizers,frozen multicourse meals, and spreads containing fish, shellfish, andother aquatic animals, but not fresh fish, containing up to about 2%Bio-PDO by weight.

Fresh eggs, including cooked eggs and egg dishes made only from freshshell eggs, containing up to about 2% Bio-PDO by weight.

Fresh fish, including only fresh and frozen fish, shellfish, and otheraquatic animals, containing up to about 2% Bio-PDO by weight.

Fresh fruits and fruit juices, including only raw fruits, citrus,melons, and berries, and home-prepared “ades” and punches madetherefrom, containing up to about 2% Bio-PDO by weight.

Fresh meats, including only fresh or home-frozen beef or veal, pork,lamb or mutton and home-prepared fresh meat-containing dishes, salads,appetizers, or sandwich spreads made therefrom, containing up to about2% Bio-PDO by weight.

Fresh poultry, including only fresh or home-frozen poultry and gamebirds and home-prepared fresh poultry-containing dishes, salads,appetizers, or sandwich spreads made therefrom, containing up to about2% Bio-PDO by weight.

Fresh vegetables, tomatoes, and potatoes, including only fresh andhome-prepared vegetables, containing up to about 2% Bio-PDO by weight.

Fruit and water ices, including all frozen fruit and water ices,containing up to about 2% Bio-PDO by weight.

Gelatins, puddings, and fillings, including flavored gelatin desserts,puddings, custards, parfaits, pie fillings, and gelatin base salads,containing up to about 2% Bio-PDO by weight.

Grain products and pastas, including macaroni and noodle products, ricedishes, and frozen multicourse meals, without meat or vegetables,containing up to about 2% Bio-PDO by weight.

Gravies and sauces, including all meat sauces and gravies, and tomato,milk, buttery, and specialty sauces, containing up to about 2% Bio-PDOby weight.

Hard candy and cough drops, including all hard type candies, containingup to about 2% Bio-PDO by weight.

Jams and jellies, home-prepared, including only home-prepared jams,jellies, fruit butters, preserves, and sweet spreads, containing up toabout 2% Bio-PDO by weight.

Jams and jellies, commercial, including only commercially processedjams, jellies, fruit butters, preserves, and sweet spreads, containingup to about 2% Bio-PDO by weight.

Meat products, including all meats and meat containing dishes, salads,appetizers, frozen multicourse meat meals, and sandwich ingredientsprepared by commercial processing or using commercially processed meatswith home preparation, containing up to about 2% Bio-PDO by weight.

Milk, whole and skim, including only whole, lowfat, and skim fluidmilks, containing up to about 2% Bio-PDO by weight.

Milk products, including flavored milks and milk drinks, dry milks,toppings, snack dips, spreads, weight control milk beverages, and othermilk origin products, containing up to about 2% Bio-PDO by weight.

Plant protein products, including the National Academy ofSciences/National Research Council “reconstituted vegetable protein”category, and meat, poultry, and fish substitutes, analogs, and extenderproducts made from plant proteins, containing up to about 2% Bio-PDO byweight.

Poultry products, including all poultry and poultry-containing dishes,salads, appetizers, frozen multicourse poultry meals, and sandwichingredients prepared by commercial processing or using commerciallyprocessed poultry with home preparation, containing up to about 2%Bio-PDO by weight.

Processed fruits and fruit juices, including all commercially processedfruits, citrus, berries, and mixtures; salads, juices and juice punches,concentrates, dilutions, “ades”, and drink substitutes made therefrom,containing up to about 2% Bio-PDO by weight.

Processed vegetables and vegetable juices, including all commerciallyprocessed vegetables, vegetable dishes, frozen multicourse vegetablemeals, and vegetable juices and blends, containing up to about 2%Bio-PDO by weight.

Snack foods, including chips, pretzels, and other novelty snacks,containing up to about 2% Bio-PDO by weight.

Soft candy, including candy bars, chocolates, fudge, mints, and otherchewy or nougat candies, containing up to about 2% Bio-PDO by weight.

Soups, home-prepared, including meat, fish, poultry, vegetable, andcombination home-prepared soups, containing up to about 2% Bio-PDO byweight.

Soups and soup mixes, including commercially prepared meat, fish,poultry, vegetable, and combination soups and soup mixes, containing upto about 2% Bio-PDO by weight.

Sugar, white, granulated, including only white granulated sugar,containing up to about 2% Bio-PDO by weight.

Sugar substitutes, including granulated, liquid, and tablet sugarsubstitutes, containing up to about 2% Bio-PDO by weight.

Sweet sauces, toppings, and syrups, including chocolate, berry, fruit,corn syrup, and maple sweet sauces and toppings, containing up to about2% Bio-PDO by weight.

INDUSTRIAL APPLICATIONS

Biologically-derived 1,3-propanediol is also useful in industrial andother miscellaneous applications wherein biodegradability is an issue.Examples of industrial applications include: agriculture, automotive,coatings, paints, inks, construction and foundry, mining, petroleum,pharmaceutical plastics, pulp & paper, rubber, synthetic lubricants,textiles and fibers, water treatment and cryogenic preservation, amongothers.

In agricultural applications, Bio-PDO can function as an irrigation aidand/or a pesticide (emulsifier, spreader, sticking agent, and foamingagent) in end uses such as pesticides (herbicide, insecticide,fungicide), fertilizers, animal feeds, and soil amendments. The generalamount of Bio-PDO in such compositions can range from about 0.1% toabout 80% by weight.

In automotive application, Bio-PDO can function as a surfactant,solvent, or thickener in end uses such as vehicle washes, waxes &polishes. The general amount of Bio-PDO in such compositions can rangefrom about 0.1% to about 50% by weight.

In coating and paint, Bio-PDO can function as a solvent, stabilizer,dispersant, or anti-freeze agent in end uses such as varnish,antimicrobials, pharmaceuticals, textiles, rubber, etc. The generalamount of Bio-PDO in such compositions can range from about 1% to about50% by weight.

In inks, Bio-PDO can function as an emulsion, polymerizer, stabilizer,dispersant and/or wetting agent in end uses such as printing andtattoos. The general amount of Bio-PDO in such compositions can rangefrom about 1% to about 50% by weight.

In mining applications, Bio-PDO can function as a lubricant, solvent, orhumectant, in end uses such as drilling and hydraulic fluid. The generalamount of Bio-PDO in such compositions can range from about 1% to about75% by weight.

In petroleum applications, Bio-PDO can function as a dessicant,emulsifier, demulsifier, corrosion inhibitor, lubricant, surfactant,biocide and/or defoamer, in end uses such as well drilling fluid, oilproduction, cementing and stimulation. The general amount of Bio-PDO insuch compositions can range from about 0.5% to about 50% by weight.

In pharmaceutical applications, Bio-PDO can function as an emulsifier,stabilizer, solvent, or antimicrobial in end uses such as drug carriers(tablets, capsules, liquids, gums). The general amount of Bio-PDO insuch compositions can range from about 0.5% to about 95% by weight.

In pulp & paper applications, Bio-PDO can function as an emulsifier,digestion, deinking, defoaming, biocide, solubilizer, or dispersant inend uses such as treatment & processing. The general amount of Bio-PDOin such compositions can range from about 0.1% to about 5% by weight.

In synthetic lubricants, Bio-PDO can functions as a cleaner, corrosioninhibitor, or lubricant in end uses such as engine compressor,hydraulics, oil drilling, metal working fluid, rolling oils, wireextrusion, plate rolling, and sheet metal processing. The general amountof Bio-PDO in such compositions can range from about 0.5% to about 50%by weight.

In water treatment applications, Bio-PDO can function as anantimicrobial, biocide, surfactant, or foam control agent in end usessuch as agriculture, pulp & paper, oil production, personal care,detergents, etc. The general amount of Bio-PDO in such compositions canrange from about 0.1% to about 50% by weight.

The Bio-PDO can also function as a humectant or in ester form inapplications such as, for example, agricultural applications to increaseuptake of actives, in tobacco handling to maintain softness, moistureretention and minimize dust formation, in ink, and in pharmaceuticaltransdermal applications; as a solvent for the spinning of poly(vinylalcohol); as a low VOC (volatile organic compound) paint stripper; as alubricant for synthetic fiber spinning; and as a stripping solution forelectronic components; as a liquid dessicant in the dehydration ofnatural gas during production and transportation.

In paint compositions, the glycol component typically is acompatabilizer, a reactive diluent or improves the applicationproperties because of its slow evaporation rate. Exemplary paintcompositions include, but are not limited to, water-based (latex)architectural coatings, especially semi-gloss paints. Glycols arepresent in the aforementioned paint compositions in amounts well knownto those of ordinary skill in the appropriate art, typically up to about20% by weight based on the weight of the total composition. A typicalformulation latex paint formulation may include, but is not limited to,the following components: 1 to 20% by weight of glycol, 20 to 60% byweight of latex emulsion, 0 to 30% by weight of fillers and up to 20% ofthe following additives: coalescing agents, surfactants, defoamers,stabilizers, biocides and thickeners.

Bio-PDO can also be used in certain biodegradable plastic applications.

Bio-PDO can further be used as a low toxic, vitrifying, bio-derivedcell/tissue/organ (for human, animal and plant) cryoprotectant material.

Esters can function as many of the above noted ingredients. While thosein those having skill in the art can readily determine which esters aremost appropriate to provide a particularly desired function,applications specifically note that esters used in this invention mayinclude the esters produced, including all the appropriate conjugatemono and diesters, from biologically-derived 1,3 propanediol usingorganic carboxylic acids. Some esters in particular that are producedinclude propanediol distearate and monostearate, propandiol dilaurateand monolaurate, propanediol dioleate and monooleate, propanedioldivalerate and monovalerate, propanediol dicaprylate and monocaprylate,propanediol dimyristate and monomyristate, propanediol dipalmitate andmonopalmitate, propanediol dibehenate and monobehenate, propanedioladipate, propanediol maleate, propanediol dioxalate, propanedioldibenzoate, propanediol diacetate, and all mixtures thereof.

The industrial compositions of the invention can contain any naturalingredients where appropriate. Natural ingredients include any naturalor nature-derived ingredients similar in composition or in function toany of the ingredients listed above.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of the present disclosurehave been described in terms of preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and methods and in the steps or in the sequence ofsteps of the method described herein without departing from the concept,spirit, and scope of the invention. More specifically, it will beapparent that certain agents, which are chemically related, may besubstituted for the agents described herein while the same or similarresults would be achieved. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope, and concept of the invention as defined by theappended claims.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the preferred features of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

Example 1

Renewably-based, biodegradable 1,3-Propanediol in Cosmetic EmulsionIngredients: % Wt. Phase A Water, deionized 61.34 Tetrasodium EDTA 0.10Bio-PDO 5.00 Carbopol 980 (2% solution) 10.00 Phase B Puresyn ® 2 5.00Lipomulse ® 165 2.50 Stearic Acid XXX 2.50 Cetearyl Alcohol 0.50Dimethicone DC 200-100 1.00 Phase C NaOH (20% solution) qs to Ph 7.0-7.51.06 Phase D Germaben II 1.00

Phase A was combined at 75° C. Phase B was combined at 75° C. Phase Bwas added to Phase A. Phase C was then added to the Phase A/B. PhaseA/B/C was cooled to 40° C. and then Phase D was added. Ph was adjustedto 7.0-7.5 with Phase C. The formulation produced was a smooth white andapparently stable emulsion.

Results—Ph 7.38, viscosity 12000 cps at 20 RPM

Oven stability was examined. Results were deemed acceptable.

Freeze/thaw stability was also examined. Freeze/thaw stability wasdeemed acceptable.

The viscosity of the cosmetic emulsion containing biologically-derived1,3-propanediol was on par with that of propylene glycol (12600 cps) andhigher than that of 1,3-butylene glycol (6000 cps) or2-methyl-1,3-propanediol (9600 cps).

Example 2

Renewably-based, biodegradable 1,3-Propanediol in Clear Face and HandLotion Ingredients: % Wt. Deionized water 66.20 Bio-PDO 16.00 Ritasail190 (RITA) (dimethicone copolyol) 2.00 Pationic ® 122A (RITA) (sodiumcaproyl lactylate 3.80 21.1% aqueous) Rhodapex ® ESY (Rhodia) (sodiumlaureth sulfate 4.00 26% aqueous) Germaben II (ISP/Sutton) (propyleneglycol, 1.00 diazolidinyl urea, methylparaben and propylparaben)Tetrasodium EDTA 5% aqueous 1.00 Aculyn ® 22 (ISP/Rohm & Haas)(acrylates/steareth-20 5.00 Methacrylate copolymer 25% aqueous)Triethanolamine 1.00 Fragrance q.s. Procedure: Ingredients are combinedin order as listed. Properties: Ph: 7.0 viscosity: 6,780 cps

Example 3

Renewably-based, biodegradable 1,3-Propanediol in Hand and Body CreamIngredients: % Wt. Deionized water 75.49 Cellosize ® PCG 10 (Amerchol)0.20 Trisodium EDTA (Universal Preserv-A-Chem) 0.10 Bio-PDO 6.50 Shebu ®Refined (RITA) (shea butter) 2.00 Arlacel ® 60 (Uniqema) 4.00 MYRJ ® 52S(Uniqema) 0.50 Glycol stearate (Stepan) 2.00 DC SF 200/350 (Dow Corning)4.00 Isopropyl palmitate (Stepan) 3.00 Vitamin A palmitate (Roche) 0.01Aloe vera gel (Bio-Botanica) 0.50 Cucumber extract (Bio-Botanica) 0.50Ginko biloba extract (Bio-Botanica) 0.50 Red Clover extract(Bio-Botanica) 0.50 Biopein ® (Bio-Botanica) 0.20 Procedure: DisperseCellosize ® PCG 10 into deionized water with mixing. Add trisodium EDTAand Bio-PDO ™ with mixing and heat to 80° C. Add the next seven itemsand continue mixing until uniform. Remove heat and allow to cool. At 30°C., add aloe vera gel, cucumber extract, ginkgo biloba extract and redclover extract. Add Biopein ® and mix until homogenous.

Example 4

Renewably-based, biodegradable 1,3-Propanediol in Moisturizing Body CareCream Ingredients: % Wt. Phase A Cremophor ® A6 (BASF) (ceteareth-6) 2.0Cremophor ® A25 (BASF) (ceteareth-25) 2.0 Vitis vinifera (grape) seedoil 6.0 Glyceryl Stearate SE 3.0 Cetearyl alcohol 2.0 Dimethicone 0.5Luvitol EHO (BASF) (cetearyl octanoate) 8.0 Oxynex ® 2004 (Merck KgaA)(1,3-Propanediol, 0.1 BHT, ascorbyl palmitate, glyceryl stearate andcitric acid) Phase B Bio-PDO 5.0 Edeta BD (BASF) (disodium EDTA) 0.1D-Panthenol USP (BASF) 1.0 Preservative q.s. Water q.s. to 100 Phase CLuvigel EM (BASF) (caprylic/capric triglycerides 1.0 and sodiumacrylates copolymer) Phase D Vitamin E Acetate (BASF) 0.5 Perfume q.s.Procedure: Heat phase A and phase B to about 80° C. Stir phase B intophase A while homogenizing. Add phase C to phase A/B and homogenizeagain. Cool to about 40° C., add phase D and homogenize shortly.Properties: Viscosity: approx. 25,000 mPa · s (Brookfield); Ph value:6.5

Example 5

Renewably-based, biodegradable 1,3-Propanediol in Moisturizing Body CareCream Ingredients: % Wt. Phase A Cremophor ® GC 7 (BASF) (PEG7-glyceryl-cocoate) 8.0 Cremophor ® A-25 (BASF) (ceteareth-25) 22.0Cremophor ® WO 7 (BASF) (hydrogenated castor oil) 1.0 Bio-PDO 3.0Masil ® SF19 (BASF) (PEG 8 methicone) 1.0 Phase B Water 65.0 Phase CPreservative q.s. Fragrance q.s. Procedure: Add ingredients in aboveorder at 80° C. and mix until uniform. Assure each is dissolved prior tonext addition. Heat phase B to 80° C. and combine with phase A. Cool to50° C. Add fragrance and preservative. Pour into containers while liquidand allow to set at room temperature.

Example 6

Renewably-based, biodegradable 1,3-Propanediol in Moisturizing Hand andBody Lotion Ingredients: % Wt. Phase A Varisoft ® TA-100 (Goldschmidt)(distearyldimonium chloride) 4.75 Crodacol C-70 (Croda) (cetyl alcohol)2.00 Penreco Snow White Petrolatum (Penreco) (petrolatum) 4.00 DC Fluid200, 1,000 cst (Dow Corning) (dimethicone) 0.25 Phase B Deionized waterq.s. Stepan ® IPM (Stepan) (isopropyl myristate) 3.25 Bio-PDO 4.00 PhaseC Sensomer ® CI-50 (Ondeo Nalco) 3.00 (starch hydroxypropyltrimoniumchloride) AA040513 Cucumber (Arylessence) (fragrance) 0.25 Preservativeq.s. Sodium hydroxide q.s. to Ph 6 Procedure: In separate containers,thoroughly mix the ingredients of phase A and phase B to 75° C. Pourphase A into phase B; mix well at temperature for 10 minutes. Removeheat and continue mixing until temperature is under 40° C. Add phase Cingredients in the order listed, mixing well between additions. AdjustPh to 6.

Example 7

Renewably-based, biodegradable 1,3-Propanediol in Moisturizing LotionSPF15 Ingredients: % Wt. Phase A Stearyl alcohol 2.00 Estol ® 1543(Uniqema) (ethylhexyl palmitate) 5.00 Estol ® 3609 (Uniqema)(triethylhexanoin) 5.00 Tween ® 60 (polysorbate 60) 2.00 Isohexadecane7.50 Solaveil ® CT100 (Uniqema) (C₁₂-C₁₅ alkyl benzoate 15.00 (and)titanium dioxide (and) polyhydroxystearic acid (and) aluminum stearate(and) alumina) Phase B Distilled water 54.40 Arlatone ® 2121 (Uniqema)(sorbitan stearate (and) 2.50 sucrose cocoate) Monomate RMEA-40 (aqua(and) disodium ricinoleamido 0.200 MEA-sulfosuccinate) Phase C Veegum ®Ultra (RT Vanderbilt) (magnesium aluminum 0.80 silicate) Keltrol ® RD(Nutrosweet Kelco) (xanthan gum) 0.20 Sodium lactate 50% 0.40 Germaben ®II (ISP) (propylene glycol (and) diazolidinyl urea 1.00 (and)methylparaben (and) propylparaben) Bio-PDO 4.00 Procedure: Heat phase Bto 80° C. with moderate stirring, until Arlatone ® 2121 is fullydispersed. Add Keltrol ® and Veegum ®; stir until homogeneous. Addremaining water phase ingredients, maintaining temperature at 80° C.Heat phase A to 80° C. Add phase A to B/C with vigorous mixing.Homogenize for two minutes. Cool with moderate stirring to roomtemperature.

Example 8

Skin Treatment Lotion Ingredients: % Wt. Phase A Deionized water 61.7Keltrol ® CG (Kelco) (xanthan gum) 0.2 Bio-PDO 5.0 Multifruit ® BSC(Arch Personal Care) 3.0 Jeescreen Benzophenone-4 (Jeen)(benzophenone-4) 0.1 Jeechem GMS-165 (Jeen) (glyceryl stearate (and) 3.0PEG-100 stearate) Phase B Jeesilc IDD (Jeen) (dimethicone crosspolymer-3(and) 4.0 isododecane) Jeesilc 245 (Jeen) (cyclomethicone) 8.0 Jeesilc200 MV (100 cst) (dimethicone) 2.0 Simulgel ® NS (Seppic) 4.0 Phase CJeesilc 6056 (Jeen) (dimethylpolysiloxane gum) 3.0 Jeecide G-II (Jeen)(propylene glycol (and) diazolidinyl urea 1.0 (and) methylparaben (and)propylparaben) Arnica Extract (Botanicals Plus) (arnica 

 rabic 

 ) 2.0 Flamingo Super Red 1.0 Phase D Jeesorb L-20 (Jeen) (polysorbate20) 1.0 Vitamin E Acetate (Jeen) (tocopheryl acetate) 0.5 Fragrance 0.5Procedure: Heat water to 65° C. Pre-mix Keltrol ® and Bio-PDO and add tothe water phase. Mix until dissolved. Add the other ingredients of phaseA one at a time and mix well. Cool to 50° C. In the oil phase tank, addthe Jeesilc IDD, Jeesilc 245 and Jeesilc 200 MV (100 cst) and mix untiluniform. Add the Simulgel ® and mix to 50° C. Using a homogenizer, addphase B to phase A and mix for 10 minutes. Cool to 40° C. Switch to propagitation. Add the ingredients of phase C one at a time into the maintank and mix well after each addition. Pre-mix phase D in a side vesseland add to the main tank. Mix well.

Example 9

Broad Spectrum SPF Sunscreen Ingredients: % Wt. Phase A Deionized water57.85 Carbopol 980 (Noveon) (carbomer) 0.30 Disodium EDTA (Dow Chemical)0.10 Bio-PDO 4.00 Phase B Escalol 557 (ISP) (octinoxate) 7.50 Escalol567 (ISP) (oxybenzone) 6.00 Escalol 517 (ISP) (avobenzone) 2.00 X-Tend226 (ISP) (2-phenylethyl benzoate) 10.00 Prolipid ® 141 (ISP) (glycerylstearate, behenyl alcohol, 4.00 palmitic acid, stearic acid, lecithin,lauryl alcohol, myristyl alcohol and cetyl alcohol) Phase C Deionizedwater 5.00 Triethanolamine 99% 0.40 Phase D Liquapar Optima (ISP)(phenoxyethanol, methylparaben, 1.25 isopropylparaben, isobutylparabenand butylparaben) Liquapar Oil (ISP) (isopropylparaben, isobutylparaben0.40 and butylparaben) Lexguard O (Inolex) (caprylyl glycol) 1.00 PhaseE Glycacil ®-L (Lonza) (iodopropynyl butylcarbamate) 0.20 Procedure:Combine ingredients in phase A; mix until uniform and heat to 75° C.Combine ingredients in phase B; heat to 75° C. Combine phase B withphase A with homogenization. Combine phase C with phase A/B withhomogenization. Cool to 45° C. (heat Lexguard O and add to LiquaParOptima) and add phase D. Add phase E. Cool to room temperature. Qs forwater loss. Properties: Viscosity: 17,600 cps, Ph 6.44\

Example 10

Standard sunscreen Ingredients % Wt. Phase A Lanolin 5.0 Homosalate 8.0White petrolatum 2.5 Stearic acid 4.0 Propylparaben 0.1 Phase BMethylparaben 0.1 Edetate disodium 0.1 Bio-PDO 5.0 Triethanolamine 1.0Purified water USP 74.3 Procedure: Preparation A and preparation B areheated separately to 77 to 82 [deg] C., with constant stirring, untilthe contents of each part are solubilized. Add preparation A slowly topreparation B while stirring. Continue stirring until the emulsionformed is cooled to room temperature (15 to 30 [deg] C.). Add sufficientpurified water to obtain 100 grams of standard sunscreen preparation.

Example 11

Water-Resistant Sunscreen Lotion SPF 21 Ingredients: % Wt. Phase ADeionized water 63.10 Versene ® NA (Dow) (disodium EDTA) 0.05 CarbopolUltrez 10 Polymer (Noveon) (carbomer) 0.25 Pemulen ® TR-2 PolymericEmulsifier (Noveon) 0.15 (acrylates/C10-30 alkyl acrylate crosspolymer)Bio-PDO 3.00 Phase B NeoHeliopan, Type AV (Haarmann & Reimer) 5.00(octyl methoxycinnamate) Octyl salicylate 3.00 HallBrite ® BHB (C.P.Hall) (butyloctyl salicylate) 5.00 Parsol ® 1789 (Roche) (avobenzone)3.00 Procol CS-20-D (Protameen) (cetearyl alcohol and ceteareth-20) 1.50Crodamol CAP (Croda) (cetearyl octanoate) 2.00 Vitamin E acetate (BASF)0.50 Phase C Crovol A-70 (Croda) (PEG-60 almond glycerides) 0.50 DC 1401Fluid (Dow Corning) (dimethiconol and 1.50 cyclomethicone) UltrasilCopolyol-1 Silicone (Noveon)(PEG-8 dimethicone) 1.50 Phenonip ®(Clariant) (phenoxyethanol, methylparaben, 1.00 ethylparaben,propylparaben, butylparaben and isobutylparaben) Tapioca Pure (NationalStarch) (tapioca starch) 4.00 Sodium hydroxide 18% 1.00 Avalure ® UR 450Polymer (Noveon) 3.95 (PPG-17/IPDI/DMPA copolymer 38% solids) Procedure:Dissolve disodium EDTA in warm water (~50° C.). Add Carbopol Ultrez 10polymer and allow to wet out for approximately five minutes. DispersePemulen ® Polymeric emulsifier and allow to mix in for about 15 minutes.Add Bio-PDO ™. Bring phase A to ~70° C. Add approximately 15% of thetotal neutralizing agent necessary to phase A. Blend phase B ingredientsand bring to ~80° C., making sure solid ingredients are dissolved. Addphase B to phase A with vigorous agitation. Add PEG-60 almondglycerides. Add dimethiconol and cyclomethicone. Add Ultrasil Copolyol-1silicone. Add Phenonip ® after the emulsion cools to <60° C. Add tapiocastarch. Add the remainder of the neutralizing agent. Add Avalure ® UR450 polymer. Ph: 7.0-7.5 Viscosity (mPa · s)*: 15,000-21,000 SPF(waterproof)**: 21 (in-vitro method, 80 min. immersion)

Example 12

Waterproof Protective Suncare SPF 20 Ingredients: % Wt. Phase A Simusol165 (Seppic) (glyceryl stearate and PEG-100 stearate) 3.20 Montanov ® S(Seppic) (coco-glucoside and coconut alcohol) 1.30 Isodecylneopentanoate 10.00 PVP □ rabic □ te □ copolymer 5.00 Bio-PDO 5.00 Ethylhexyl methoxycinnamate 7.50 Benzophenone-3 2.50 Ethyl hexyl salicylate5.00 Zinc oxide 7.10 Phase B Sepicalm VG (Seppic) (sodium palmitoyl 

 rabic 

3.00 and Nymphea alba flower extract) Cyclomethicone 5.00 Phase CSimulgel ® EG (Seppic) (sodium 1.00 acrylate/acryloyldimethyltauratecopolymer, isohexadecane and polysorbate 80) Phase D Tromethamine q.s.Tetrasodium EDTA 0.20 Xanthan gum 0.15 Magnesium aluminum silicate 1.00Water q.s. to 100 Phase E Sepicide HB (Seppic) (phenoxyethanol (and)methylparaben 0.30 (and) ethylparaben (and) propylparaben (and)butylparaben) Sepicide CI (Seppic) (imidazolidinyl urea) 0.20 DL-alphatocopherol 0.05 Fragrance 0.30 Procedure: Melt phase A ingredients at75-80° C. and disperse zinc oxide in the warm fatty phase. Dispersesilicate and xanthan gum in water until homogeneous, then introduce EDTAand tromethamine. Add Simulgel ® EG to this blend with vigorous stirringto obtain swelling of the polymer, then heat to 80° C. Add fatty phase Ato the water phase and begin homogenizing for five minutes. Startcooling while continuously homogenizing. Introduce Sepicalm VG andcyclomethicone at 60° C. and homogenize for five minutes. Cool withmoderate stirring and add phase E ingredients at 30° C.

Example 13

Hand Barrier Cream Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0Bio-PDO 4.00 Ammonyx ® GA-70PG* 2.86 Phase 2 Petrolatum 4.00 Stepan ®IPP 3.00 Stepan ® Cetyl Alcohol, NF 2.00 TiO2Sperse 40% solution inOctyldodecyl Neopentanoate 10.00 (Collaborative Labs) Phase 3 KCl 0.40Citric Acid q.s. Preservatives q.s. Total 100.00 Procedure: Preparewater phase by adding water, Bio-PDO ™ and Ammonyx ® GA-70PG*. Mix well.Start heating to 160° F. Prepare oil phase by adding Petrolatum,Stepan ® IPP, Stepan ® Cetyl Alcohol and TiO2Sperse. Heat to 160-165° F.Add oil phase to the water phase. Emulsify for 20-25 minutes. Cool toroom temperature. Premix KCl with water and add to batch. Addpreservatives. Adjust Ph to 4.0 if necessary. Physical Properties Ph4.0-5.0; Viscosity 2,000-3,000 cps

Example 14

Lotion for Normal-Oily Skin Ingredients: % Wt. Phase 1 D.I. Water q.s.to 100.0 Carbopol 934 (BF Goodrich) Carbomer 0.15 Bio-PDO 3.00 Phase 2Stepan ® Octyl Isononanoate 5.00 Dow Corning 200 Fluid (Dow Corning)Dimethicone 0.10 Wecobee ® S 0.50 Stepan ® Cetyl Alcohol, NF 0.50Kartacid 1890 (Akzo Nobel BV) Stearic Acid 3.00 Phase 3 Versene ® 200(Dow Corning) Tetrasodium EDTA 0.10 Triethanolamine 1.80 Preservativeq.s. Total 100.0 Procedure: Prepare Phase 1 by adding D.I. water to asuitable mixing vessel and begin agitation. Add Carbopol 934 with goodagitation and mix at high speed until the solution is free of lumps. AddBio-PDO ™ and mix. Heat to 165-170° F. In a separate container preparePhase 2 and heat to 170-175° F. Add Phase 2 to Phase 1 with goodagitation and mix for 30 minutes. Start cooling to 90° F. At 110° F. addPhase 3 ingredients. Stop cooling and agitation at 90° F. Properties:Viscosity at 25° C.: 2000-5000 cps; Ph 7.8-8.0

Example 15

Skin Soothing Lotion Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0Carbopol 940 (B.F. Goodrich) Carbomer 0.20 Glucam ® P-20 (Amerchol)PPG-20 Methyl Glucose Ether 0.14 Bio-PDO 2.25 Phase 2 Neobee ® M-20 4.50Wecobee ® S 0.75 Stepan ® 653 0.50 Stepan ® Cetyl Alcohol, NF 0.50Kartacid 1890 (Akzo Nobel BV) Stearic Acid 2.95 Phase 3 Preservative0.10 Versene ® 220 (Dow) Tetrasodium EDTA 0.10 Triethanolamine 0.25Total 100.0 Procedure: Prepare Phase 1. Add Carbopol 940 to D.I. waterwith good mixing until solution is free of lumps. Add PPG-20 methylglucose ether and Bio-PDO ™. Mix until completely dissolved. Heat to165° F. In a separate container, prepare Phase 2. Heat to 165-170° F.Add Phase 2 to Phase 1 (both at 165-170° F.) with good agitation.Emulsify for 20 minutes and then begin to cool with slow agitation. At110° F. add ingredients from Phase 3. At 90° F. stop cooling andagitation. Properties: Viscosity: at 25° C.: 2200-3700 cps

Example 16

Clear Moisturizer Ingredients: % Wt. Aloe Vera Gel q.s. to 100.0 Bio-PDO3.50 Methyl Paraben 0.15 Carbopol 934 0.50 Alcohol 190 Proof 20.00Stepan ® PEG 600 ML 1.00 Tween ® 2.00 Fragrance q.s. TEA 88% 0.8 Glydantq.s. Total 100.0 Procedure: Combine Aloe Vera Gel and Bio-PDO ™. Startmixing. Add methyl paraben. Mix until solution is clear. Add Carbopol934. Mix until solution does not have lumps. Add alcohol. Mix well.Premix PEG 600 Monolaurate, Tween 20 and perfume. Add to batch. Mixwell. Add Glydant. Add TEA. Solution should be clear. PhysicalProperties: Ph 6.0-6.5

Example 17

Therapeutic Hand & Body Lotion Ingredients: % Wt. Phase 1 D.I. Waterq.s. to 100.0 Bio-PDO 4.00 Ammonyx ® GA-70PG 18.4 Phase 2 Petrolatum 4.0Stepan ® IPP 3.0 Silicone DC-200 (350 cps) 1.0 Stepan ® Cetyl Alcohol,NF 2.0 Phase 3 KCl 0.4 Citric Acid q.s. Glydant q.s. Total 100.0Procedure: Prepare water phase by adding water, Bio-PDO ™, and Ammonyx ®GA-70PG. Mix well. Start heating to 160° F. Prepare oil phase by addingpetrolatum, Stepan ® IPP, silicone, Stepan ® Cetyl Alcohol. Heat to160-165° F. Add oil phase to water phase. Emulsify for 20-25 minutes.Start cooling. Premix KCl with water and add into the batch at 100-110°F. Add Glydant at 100° F. Adjust Ph if necessary. Homogenize ifnecessary. Physical Properties: Ph 4.0-4.5; viscosity: 3,000-4,000 cps

Example 18

Cream Conditioner for Permanent-Waved Hair Ingredients: % Wt. Ammonyx ®4 5.00 Bio-PDO 1.50 Panthenol 0.50 Citric Acid q.s. D.I. Water q.s. to100 Stepan ® Cetyl Alcohol, NF 2.50 PPG-Ceteth 20 1.25 Stepan ® StearylAlcohol 97 0.75 Fragrance, Dye & Preservative q.s. Total 100.0Procedure: Add ingredients and mix while heating to 75° C. Mix untilwell blended. Cool with mixing to 30° C. and add fragrance,preservative, and dye if desired. Adjust Ph with citric acid to 3-5.Physical Properties: Appearance: Opaque, white liquid; Viscosity: 2000cps

Example 19

Clear Hair Conditioner Ingredients: % Wt. Ammonyx ® KP 3.00 Ammonyx ®CETAC 1.50 Bio-PDO 1.50 Hydroxyethylcellulose 0.90 Polyquaternium 100.25 Fragrance, Dye & Preservative q.s. Citric Acid q.s. D.I. Water q.s.to 100 Total 100.0 Procedure: Disperse hydroxyethylcellulose in D.I.water with mixing until clear. Add Ammonyx ® KP and mix untilhomogeneous. Slowly add Ammonyx ® CETAC and mix until homogeneous.Disperse Polyquaternium-10 in Bio-PDO and add to above solution withmixing until clear. Adjust Ph to 5.5, if necessary, with citric acid.Add fragrance, dye and preservative, if desired. Physical Properties: Ph5.5; viscosity: 750 cps

Example 20

Spray-On Detangling Conditioner Ingredients: % Wt. D.I. Water q.s. to100.0 Bio-PDO 1.50 Ammonyx ® KP 1.00 Surfactant 193 (Dow Corning)Dimethicone Copolyol 1.00 Tween ® 20 (ICI) Polysorbate-20 0.30 CitricAcid (50%) q.s. Fragrance, Dye & Preservative q.s. Total 100.0Procedure: Into a vessel equipped with agitation, add first fouringredients. Mix well. Premix fragrance and Tween ® 20 in a separatecontainer. Add to the batch. Mix well. Adjust Ph with citric acid, ifnecessary. Add dye and preservative as desired. Physical Properties: Ph4.0-4.4; Viscosity at 25° C.: water thin

Example 21

Moisturizing Spray Ingredients: % Wt. Water 70.8 Preservative 0.2Bio-PDO 28.0 Ammonyx ® GA-70PG 0.9 Hydrolyzed Silk 0.1 Fragrance 0.1Total 100.0 Procedure: Charge water. Add Bio-PDO ™. Heat to 50° C. andblend in Ammonyx ® GA-70PG. Mix well until homogeneous. Cool withmixing. At 30° C., add propyl paraben and hydrolyzed silk. Cool to 25°C., add fragrance. Adjust Ph to 5.5-6.5 with citric acid or sodiumhydroxide. Physical Properties: Viscosity: 20 cps

Example 22

Men's After Shave—Clear Microemulsion Ingredients: % Wt. Phase 1Stepan ® PEG 400 MO 12.7 Stepan ® IPM 11.0 Stepan ® PEG 400 ML 7.0Bio-PDO 3.5 Stepan ® GMO 3.0 DC 556 Silicone Fluid (Dow Corning) 1.0Phase 2 Ethanol 25.0 Triethanolamine q.s. Fragrance, dye, preservativeq.s. D.I. Water q.s. to 100 Total 100.0 Procedure: Heat D.I. water to95° C. Mix the components of Phase (1) and heat to 95° C. Add Phase (1)to D.I. water with mixing. Cool to 30° C., and add ethanol. Adjust Ph to7.0-8.0 with triethanolamine. Add fragrance, dye, and preservative, ifdesired. This formula will create a clear microemulsion. PhysicalProperties: Ph 7.0-8.0; viscosity: 40 cps

Example 23

Hand Cleanser Ingredients: Wt. % Ammonium Lauryl Sulfate (ALS) (28%)26.0 Cocamide DEA 6.0 Sodium Lauryl Sulfate (SLS) (25%) 18.0 Bio-PDOPropanediol 1.0 Water 44.5 Bio-PDO Stearate 0.5 Irgasan 0.2 TetrasodiumEDTA (5 wt %) 2.0 Fragrance 0.2 Citric acid (50 wt %) QS Procedure BlendALS, Cocamide DEA, SLS and Zemea ™ Propanediol Add Bio-PDO Stearate andIrgsan Heat to 60 Oc. Cool to 30 Oc, add EDTA Stir until a homogeneoussolution is formed Adjust to Ph 6 with citric acid Add fragranceBenefits Highly Stable Higher Viscosity Excellent Foaming

Example 24

Hand Cleanser Ingredients: Wt. % Carbopol 934 NF 0.50 Germaben II 0.06Bio-PDO 5.00 Isopropyl alcohol (IPA) 47.70 D. I. Water 43.79Triethanolamine (20 wt %) 2.50 Fragrance 0.50 Procedure Heat water andgermaben II solution at 50 Oc Add carbopol Stir contents to form uniformgel Add Bio-PDO, IPA and water Stir until a homogeneous solution isformed Cool below 30 Oc Adjust to Ph 7 with TEA Add fragrance BenefitsHighly Stable Higher Viscosity Excellent Hydrotrope

Example 25

Hair Conditioner Ingredients Wt % Ammonyx^(R) 4⁴ 5.00 Bio-PDO ¹ 1.50Panthenol 0.50 Cetyl alcohol² 3.50 Ceteareth³ 1.25 Germaben II ² 0.50Fragrance, Dye QS D. I. Water QS to 100 ¹ DuPont Tate & Lyle BioProducts ²The Chemistry Store.com, Cayce, SC ³Somerset Cosmetic Co. LLC,Renton, WA ⁴Stephan Co. Northfield, IL Procedure: Combine componentslisted in the table, mix well and heat to 75° C. Mix until well blended.Cool mixture and add preservative. Adjust the Ph to 5, if required usingcitric acid. Mix the mixture overnight. Opaque white liquid is formed.Physical Properties: Ph: 5; Opaque white liquid is formed.

Example 26

Hand Cleanser Ingredient Wt. % Carbopol 934 NF ² 0.50 BioPDO ¹ 5.00Isopropyl alcohol 57.0 D. I. Water 35.0 Triethanolamine (20 wt %) 2.0Fragrance QS ¹ DuPont Tate & Lyle Bio Products ² Noveon, Cleveland, OHProcedure: Heat the 100 g water to 50° C. and add this hot solution to 4g Carbopol 940. Stir the gel at 50° C. for 4 h. Stop heating andcontinue the agitation for 20 h. A uniform gel will formed. Add theBio-PDO, Isopropyl alcohol and water, agitate until a homogenous mixtureis formed and cool the Adjust the Ph to 7 using dilute triethanolaminesolution. Add fragrance. Mixture should be clear after Ph is adjusted.

Example 27

Solid Deodorant Ingredients Wt % Bio-PDO ¹ 48.0 Sodium stearate 6.5Poly(ethylene glycol) monolaurate ⁶ 2.0 Irgasan ⁶ 0.2 Water QS ¹ DuPontTate & Lyle Bio Products ⁶ Sigma-Aldrich, Milwaukee, WI Procedure: Tothe mixture of Bio-PDO and water add sodium stearate and heat it to 100°C. until a clear liquid is formed add PEG monolaurate. Cool the mixtureto 50° C. and pour into containers.

Example 28

Clear Tanning Spray Gel Ingredients Wt % Phase A D.I water 12.5 Carbopol934⁵ 0.5 Germaben II² 0.05 Phase B Bio-PDO¹ 5.0 Ethanol 20.0Poly(ethylene glycol) monolaurate⁶ 1.0 Polysorbate 60³ 2.0 Phase C2-Phenyl-5-benzimidazolesulfonic acid⁶ 2.0 Triethanol amine 2.0 D.I.water 25.0 Phase D D.I water QS Germaben II² 0.8 ¹DuPont Tate & Lyle BioProducts ²The Chemistry Store.com, Cayce, SC ³Somerset Cosmetic Co. LLC,Renton, WA ⁴Stephan Co. Northfield, IL ⁵Noveon, Cleveland, OH⁶Sigma-Aldrich, Milwaukee, WI Procedure: Mix water and Germaben II ofphase and heat the mixture to 50° C. and add this hot solution toCarbopol. Stirr the gel at 50° C. for 4 h. Stop heating and continue theagitation for 20 h. In a separate container, take2-Phenyl-5-benzimidazolesulfonic acid, add water and triethanolamine.Mix the components until a clear solution is formed. Add Bio-PDO,ethanol PEG monolaurate and polysorbate 60. Mix until a uniform gel isformed. Add phase C, mix the gel thoroughly. Add water and preservativecontinue agitation until a clear gel is formed. Ph should be about 7.

Example 29

Men's After Shave Ingredients Wt % Phase A Poly(ethylene glycol)monooleate⁶ 17.5 Aloe Vera 5.0 Poly(ethylene glycol) monolaurate⁶ 7.0Bio-PDO¹ 5.0 Sorbitol³ 3.0 Panthenol 0.5 Phase B Ethanol 25.0GermabenII² 0.5 Triethanol amine, Fragrance, dye QS Water QS to 100Viscosity 21 cps ¹DuPont Tate & Lyle Bio Products ²The ChemistryStore.com, Cayce, SC ³Somerset Cosmetic Co. LLC, Renton, WA ⁴Stephan Co.Northfield, IL ⁵Noveon, Cleveland, OH ⁶Sigma-Aldrich, Milwaukee, WIProcedure: Combine components of phase A and heat to 80° C. Add waterand heat to 80° C. Cool to 30° C. and add ethanol. Adjust the Ph to7.0-8.0 with triethanolamine, if required Add fragrance, dye andpreservative.

Example 30

Skin Lotion Ingredients Wt % Phase A D.I. Water 20 Carbopol 934 NF⁵ 0.15Bio-PDO¹ 3.00 Phase B Stephan IPM⁴ 5.00 Dimethicone³ 0.10 Cetyl Alcohol²0.50 Stearic acid 3.00 Phase C Triethanolamine 1.80 Tetrasodium EDTA(5%) 4.00 Preservative Q.S. D.I. Water Q.S. to 100 Physical Properties:Ph 7.5; Viscosity: #4@ 60 rpm 2240 cps ¹DuPont Tate & Lyle Bio Products²The Chemistry Store.com, Cayce, SC ³Somerset Cosmetic Co. LLC, Renton,WA ⁴Stephan Co. Northfield, IL ⁵Noveon, Cleveland, OH Procedure: Combinecomponents of phase A, mix well and heat to 80° c. Combine Stephan IPM,dimethicone and cetyl alcohol in a different container and heat themixture to 80° c. until a clear solution is formed. Add stearic acid tophase B and heat the mixture again at 80° c. until a clear solution isformed. Combine the Phase A and Phase B until well blended Cool themixture to 50° c. and add triethanol amine and tetrasodium EDTAsolution. Heat the mixture until mixture is well blended. Cool themixture and add required amounts of water and preservative.

Example 31

Clear Moisturizer Ingredients Wt % Phase A Aloe Vera Gel QS to 100Bio-PDO¹ 3.5 Carbopol 934⁵ 0.5 Ethanol 20 PEG 1.0 Triethanol amine 0.8Fragrance Qs Germaben II² 0.2 ¹DuPont Tate & Lyle Bio Products ²TheChemistry Store.com, Cayce, SC ⁵Noveon, Cleveland, OH Procedure: CombineAloe Vera Gel, Bio-PDO and GermabenII. Mix until the solution is clear.Add Carbopol. Heat the mixture to 60° C. with stirring until thesolution does not have lumps. Add alcohol. Mix well. Add PEG. Mix welluntil it forms clear solution. Add perfume, TEA and preservative.

Example 32

Clear Shampoo Ingredients Wt % Blend 213² 25 Sodium Laureth SulfateCocamidopropyl Betaine Cocamide DEA PEG-150 Distearate CocamidopropylBetaine² 5 Bio-PDO¹ 5 DI Water 65 Sodium chloride solution (25 wt %) QS¹DuPont Tate & Lyle Bio Products ²The Chemistry Store.com, Cayce, SCProcedure: Mix Blend 213 and cocamidopropyl betaine, add BioPDO, mixwell. Add water and stir for 20 h. Adjust the viscosity with sodiumchloride solution, if required.

Example 33

Kid's Soap with Antibacterial Agent Ingredients Wt % Phase A CustomBlend BSC 40.0 Bio-PDO¹ 2.0 Chloroxylenol 0.75 Phase B NaCl (25 wt %)solution 1.00 D.I Water, Fragrance QS ¹DuPont Tate & Lyle Bio Products⁷Custom Ingredients, Inc. Chester, SC Properties: Ph: 7; Viscosity: 3000cps Procedure: Combine components of phase A and mix well. Apply heat tocompletely dissolve and achieve a clear solution. Add warm water slowlyand heat to clarity. Cool very slowly with mixing. Adjust the viscositywith sodium chloride. Add desired fragrance.

Example 34

Foundation SEQ INGREDIENT % Wt A Deionized Water 63.00 A CMC 7H3SF 0.30A Veegum Ultra Granules 0.35 A Alcolec S (Lecithin) 0.40 ATriethanolamine 99% 1.25 A Bio-PDO (1,3 Propanediol) 6.00 B TitaniumDioxide (water dispersible 8.00 B Red Iron Oxide 0.40 B Yellow IronOxide 0.80 B Black Iron Oxide 0.10 B Collodial Kaolin 2.00 B MethylParaben 0.20 C Permethyl ® 102A (Isoeicosane) 10.00 C Isostearic Acid1.00 C Stearic Acid Triple Pressed 2.50 C LIPO GMS 450 (GlycerylMonostearate) 1.50 C Liponate TDTM (Tridecyl Trimelitate) 1.00 C LIPOGMS 470 (Glyceryl Monostearate) 1.00 C Propyl Paraben 0.20 FORMULATOTALS: 100.00

The manufacturing procedure for this emulsion was typical for alloil-in-water type products. Sequence A was dispersed and when the gumswere completely hydrated and the phase was uniform, pre-ground SequenceB (pigment phase) was added to it and mixed until both phases werecompletely uniform and homogeneous. Sequence C was weighed in a separatevessel and heated to 75°-80° C. until all the solids were melted and thephase was uniform. Sequence A was then heated to 75°-80° C. When all thephases were all at the proper temperatures, Sequence C (oil phase) wasslowly added to Sequences A & B (water phase). The emulsion was allowedto mix at 75° C. for 15 minutes and then cooled to 25° C. Samples fortesting were then poured off and placed at their respective stabilitystations in preparation for the 4 week study. The color and powder fillloading in these formulations was kept constant at 11.30% dry pigment.Conventional powder fill ingredients were chosen for these formulationsas to eliminate any potential variability in test results.

Physical Testing: Brookfield Model RV - Spindle 5 at 20 rpm for 1 minute(factor × 200) Iinitial Iinitial 1 week 2 week 2 week 3 week 4 week 4week Ph Viscosity Viscosity Ph Viscosity Viscosity Ph Viscosity 8.032400 2900 7.94 2900 2900 8.02 2900

Viscosity readings throughout the 4 week test period showed that therewas no unusual build or decrease in viscosity. Oven stability consistedof R/T, 45° C., and 2 Freeze/Thaw cycles. After 4 weeks, samples showedno signs of separation, sweating, severe loss of viscosity, change inconsistency, loss of structure, odor problems, or color change at anytemperature.

Aesthetic Properties

All samples were evaluated for potential differences in odor, color,appearance, application, texture, feel, wearability, or any otherdifferences, if any. All foundation samples were evaluated side-by side.In no cases were there any perceivable differences in any of theaesthetic properties associated with these types of cosmetic properties.Any differences noticed were insignificant and were not a result of theingredient changes. These were all fragrance free formulations, andthere were no apparent odor differences in any of the samples.

Example 35

Mascara SEQ INGREDIENT % Wt. A Deionized Water 49.00 A Xanthan Gum 0.15A Veegum HV Granules 0.55 A Disodium EDTA 0.05 A Triethanolamine 99%0.50 A Alcolec S (Lecithin) 0.20 A Methyl Paraben 0.30 A Bio-PDO 10.00 BBlack Iron Oxide 9.00 C DC 345 Fluid (D5 Cyclomethicone) 4.50 C DC5225CFormulation Aid 0.90 C White Beeswax 7.25 C Carnauba Wax #1 3.50 CStearic Acid Triple Pressed 1.80 C Lipomulse 165 (Glyceryl 1.80Monostearate) C Indopol H100 (Polybutene) 3.50 C Phenoxyethanol 1.00 CPropyl Paraben 0.20 C PVP/Eicosene Colpolymer 4.00 C Lipocol S (StearylAlcohol) 1.80 FORMULA TOTALS: 100.00

The manufacturing procedure for this formula was similar to that of thefoundation in Example 24. Higher temperatures were required for the oilphase due to the high level of hard waxes employed in this product.Sequence A was dispersed and when the gums were completely hydrated andthe phase was uniform, pre-ground sequence B (pigment phase) was addedto it and mixed until both phases were completely uniform andhomogeneous. Sequence C was weighed in a separate vessel and heated to80°-85° C. until all the solids were melted and the phase was uniform.Sequence A was then heated to 75°-80° C. When all the phases were all atthe proper temperatures, Sequence C (oil phase) was slowly added toSequences A & B (water phase). The emulsion was allowed to mix at 75° C.for 15 minutes. When the batch began to thicken at around 45° C., apaddle mixer was used to adequately turn over and mix the batch. Thebatch was mixed and cooled to 35° C. Samples for testing were thenpoured off and placed at their respective stability stations inpreparation for the 4 week study. The color loading in theseformulations was kept constant at 9.00% dry pigment. No other powderfill, except for the black iron oxide pigment, was employed in theseformulations. Additional powder fills will lend to a whitening andashyness, which, in mascaras, is unacceptable.

Physical Testing Brookfield Model RV - Spindle T at 5 rpm for 1 minute(factor × 10,000) Initial 1 week 2 week 2 week 3 week 4 week 4 weekInitial Ph Viscosity Viscosity Ph Viscosity Viscosity Ph Viscosity 8.58180,000 320,000 8.55 380,000 430,000 8.55 420,000

Viscosity readings throughout the 4 week test period showed that therewas no unusual build or decrease in viscosity. The variations seen arevery typical for a product of this type and fall within an acceptablerange for a mascara type product. Oven stability consisted of R/T, 45°C., and 2 Freeze/Thaw cycles. After 4 weeks, samples showed no signs ofseparation, sweating, severe loss of viscosity, change in consistency,loss of structure, odor problems, or color change at any temperature.

Aesthetic Properties:

All samples were evaluated for potential differences in odor, color,appearance, application, texture, feel, wearability, or any otherdifferences, if any. All mascara samples were evaluated side-by side. Inno cases were there any perceivable differences in any of the aestheticproperties associated with these types of cosmetic properties. Anydifferences noticed were insignificant and were not a result of theingredient changes. Additionally, the mascara samples showed nodifferences in water resistance. Even though the mascara was notspecifically designed to be water resistant, side by side, the productsperformed equally. These were all fragrance free formulations, and therewere no apparent odor differences in any of the samples.

Example 36

Body Wash Ingredients: % Wt. Water 45.0 Ammonium Lauryl Sulfate, 25%21.0 Ammonium Laureth Sulfate, 28% 21.0 Cocamidopropyl Betaine, 35% 4.0Acrylates Copolymer, Structure 3001 (30%) 5.0 Bio-PDO 1.0 Glycerin 1.0PEG 10 Sunflower Glycerides 0.5 Soybean Oil 0.2 Fragrance (0.2) CocamideMEA 0.2 PEG 5 Cocamide 0.2 Guar Hydroxypropyl trimonium Chloride 0.2Diisopropanolamine 0.1 Methylcellulose 0.05 Carbomer 0.05 TetrasodiumEDTA 0.05 Methylchloroisothiazolinone, Methylisothiazolinone 0.05Etidronic Acid 0.05 Guanine (CI 75170) 0.05 Mica (CI 77019) 0.05Titanium Dioxide (CI 77891) 0.05 TOTAL 100

Ingredients were combined in the following order, with propeller mixeragitation, allowing each ingredient to dissolve, disperse completelybefore adding the next. Batch was processed at 60° C.: Water, Acrylatespolymer, ALS, ALES, GAB, Guar Hydroxypropyl trimonium Chloride, EDTA,PEG 10 Sunflower glycerides, soybean oil, cocamide MEA, PEG 5 cocamide,iisopropanolamine/methylcellulose/carbomer/guanine, mica/titanium oxide,glycerin.

Example 37

Baby Lotion Ingredients: % Wt. Water 85.2 Bio-PDO 3.0 Myristyl Myristate2.5 Glyceryl Stearate 1.5 Oleic Acid 1.2 Stearic Acid 1.2 Polysorbate 610.6 C12-15 Alkyl Benzoate 0.5 Dimethicone 0.5 Isopropyl Palmitate 0.5Sorbitan Stearate 0.5 Cetyl Alcohol 0.5 Synthetic Beeswax 0.5 StearylAlcohol 0.5 Benzyl Alcohol 0.4 Carbomer 934 0.4 Fragrance 0.1Methylparaben 0.2 Propylparaben 0.05 Butylparaben 0.05 BHT 0.05 D&C Red3 trace TOTAL 100

Ingredients were combined in the following order, allowing each todissolve/disperse completely before adding the next:

Phase A: Disperse Carbomer in water with high speed agitation, allowingparticles to wet completely. Add Bio-PDO. Heat to 70° C.

Phase B: Combine Myristyl Myristate, glyceryl stearate, Oleic Acid,Polysorbate 61, C12-15 Alkyl Benzoate, Dimethicone, Isopropyl Palmitate,Sorbitan Stearate, Cetyl Alcohol, Synthetic Beeswax, Stearyl; Alcohol,Benzyl Alcohol, Methylparaben, Propylparaben, Butylparaben, and BHT,heat to 70° C.

With continuous high speed agitation, slowly add Phase B to Phase A toform emulsion. Remove from heat and begin cooling with continuedagitation. After several minutes of mixing, add NaOH, dissolved in asmall amount of water. Batch will thicken. When Batch reaches roomtemperature, add color, fragrance, and replace water lost toevaporation. Batch is complete.

Example 38

Sulfate-Free Shampoo Phase Ingredients: % Wt. A Water 33.82 A NA₂EDTA0.05 A BIOTERGE AS 40 45.00 A GLUCAMATE DOE 120 1.50 A Bio-PDO 4.75 BMONAMID CMA 3.00 B VELVETEX BK 35 10.00 C KATHON CG 0.06 C MACKPEARL140V 1.50 D CITRIC ACID, 20% SOLN TO PH 6.0-6.5 0.32 TOTAL 100.00Manufacturing Process: Phase A: Combine Phase A ingredients into waterand heat with mixing to 75° C. Slowly add remaining Phase A ingredients.Hold temperature at 75° C. and mix slowly. Phase B: Combine phase Bingredients and heat to 75° C. with slow mixing. Add Phase B to Phase Aand mix until uniform. Phase C: Add Phase C one at a time Phase D: UsePhase D to adjust the Ph of batch to 6.0-6.5

Example 39

Colored cosmetic composition (liquid make-up) Ingredients Wt % Phase ATitanium Dioxide 6.0 Iron Oxide, red 1.0 Pigment Blend 5 0.5 BourdauxMica 0.5 Caster Oil 8.0 Phase B Water 46.9 Bio-PDO 22.0 Emulsifying Vax9.0 Sodium Stearate 4.5 GelMaker EMU 1.3 Methylbaraben 0.3 Preparation:Mix the ingredients of phase B (aqueous phase) and heat the mixture to65° c. with thorough stirring to form a homogeneous aqueous phase.Separately mix the contents of phase A until a uniform gel is formed.Mix phase A and phase B and heat the mixture while stirring at 65° c.for 1 hour. Cool the composition and transfer into containers. Stableoil in water emulsions were obtained.

Example 40

Colored cosmetic composition (liquid make-up) Ingredients Wt % Phase ATitanium Dioxide 5.0 Iron Oxide, red 1.0 Pigment Blend 5 0.5 BourdauxMica 0.5 Caster Oil 9.0 Phase B Water 46.9 Bio-PDO 22.0 Emulsifying Vax9.0 Sodium Stearate 4.5 GelMaker EMU 1.3 Methylbaraben 0.3 Preparation:Mix the ingredients of phase B (aqueous phase) and heat the mixture to65° c. with thorough stirring to form a homogeneous aqueous phase.Separately mix the contents of phase A until a uniform gel is formed.Mix phase A and phase B and heat the mixture while stirring at 65° c.for 1 hour. Cool the composition and transfer into containers. Stableoil in water emulsions were obtained.

Example 41

EYE MAKEUP REMOVER INGREDIENT Weight Percent C13-15 Alkanes (Gemseal ®25) 5.00 C15-19 Alkanes (Gemseal ® 40) 10.00 Oleth-5 13.00 DEA Oleth-3Phosphate 5.75 Deionized Water 47.45 Bio-PDO 12.00 Glycerin 99% 6.50Germaben II-E 0.30

Manufacturing Procedure:

Weigh the ingredients in Sequence A in a suitable vessel. Begin heatingto 75-80° C. with good mixing. Weigh ingredients in Sequence B in asecondary vessel. Begin heating to 75-80° C. with good mixing. When bothsequences are at the proper temperatures, slowly add Sequence B toSequence A with continuous propeller mixing. Increase mixer speed as thesequences are combined. Switch to a side wiping mixer and continuemixing until the batch is smooth, uniform and homogeneous. Mix for 15minutes and begin cooling the batch with continuous mixing. Cool thebatch to 25° C. At 25° C., remove the batch and store in airtightcontainers. Check the viscosity and Ph of the batch.

Example 42

Eye Shadow Ingredient Weight Percent Deionized Water 44.15 Keltrol F0.20 Veegum Regular Granules 2.00 Disodium EDTA 0.10 Triethanolamine 99%0.50 Bio-PDO 10.00 Lubrajel Oil 1.00 Isodecyl Neopentanoate 7.35 LipoGMS 450 2.00 Behenyl Alcohol 0.50 Myristyl Alcohol 0.50 Cetyl Alcohol0.50 Stearic Acid 1.50 Alcolec S 0.15 Isostearyl Neopentanoate 5.00Tocopheryl Acetate 0.05 Allianz ™ OPT 1.00 DC 345 Fluid-Cyclomethicone7.50 Germaben II-E 1.00 Cosmetic Russet C33-5138 0.60 Cosmetic YellowC33-1700 0.12 Black Iron Oxide LC989 0.24 Sericite PHN 0.24 TimicaSparkle 110P 13.80

Manufacturing Procedure:

Combine ingredients in Phase A and begin mixing until the Phase issmooth and uniform. Combine Phase B ingredients and begin heating to 80°C. with continuous mixing. Heat Phase A to 75-80° C. When Phase A andPhase B are at the proper temperatures slowly add Phase B to Phase Ausing continuous high speed homogenizing mixing. Add Phase C to thebatch with homogenizing mixing. When the batch is uniform, begin coolingthe batch to 55° C. with continuous homogenizer mixing. At 55° C. addPhase D to the batch. Mix until uniform. Add Phase E to the batch andmix until uniform. Weigh Phase F in a suitable blender. Grind Phase Fthrough a micropulverizer or equivalent. When Phase F is free of pigmentspecks, add Phase G to Phase F and blend until uniform. In the mainbatch vessel, switch to a side wiping mixer and begin cooling the batchto 25° C. At 25° C. add Phase F & G to the batch and mix until all thepowders are dispersed and batch is smooth and uniform. Store the batchin airtight containers until ready for filling. Check the viscosity andPh of the batch.

Example 43

Cheek Color Ingredients Weight Percent Deionized Water 62.00 Bio-PDO8.00 Stepanquat ML 2.00 Germaben II-E 1.00 SI-TEC ™ CM-040 20.00Cyclomethicone Abil EM-90 1.00 Salcare SC-95 2.00 Phenoxyethanol 1.00SI-TEC ™ CM-040 1.80 Cyclomethicone Titanium Dioxide 328 0.68 D&C Red 30(Puricolor 0.52 Red VRE1)

Manufacturing Procedure:

NOTE: This is a cold process emulsion and must be manufactured at roomtemperature (25° C.). Combine Phase A in a suitable mixing vessel. Mixuntil the Phase is clear and uniform. Combine Phase B in a suitablemixing vessel. Mix until the Phase is clear and uniform. Premix Phase Cin a separate container and grind through a 3-roll mill until there areno pigment specks present. Add Phase C to Phase B and mix until all thecolor is dispersed. When Phases A and B & C are uniform, slowly addPhase A to combined Phases B & C and mix until all the phases arecombined. Switch to a homogenizing mixer and mix for 10-15 minutes.Store the batch in airtight containers until ready for filling. Checkthe viscosity and Ph of the batch.

Example 44

Liquid Eyeliner Ingredients Weight Percent Deionized Water 35.00 KeltrolF 0.20 Methyl Paraben 0.25 PVP K-30 (10% Aq Solution) 11.75Triethanolamine 99% 1.00 Bio-PDO 10.00 Cosmetic Russet C33-5138 5.00Cosmetic Yellow C33-1700 1.00 Black Iron Oxide LC989 2.00 Sericite PHN2.00 Carnauba Wax #1 4.00 White Beeswax 2.00 Permethyl 104A 6.00 StearicAcid 2.50 Lipo GMS 450 1.00 Propyl Paraben 0.20 Phenoxyethanol 1.00Deionized Water 1.00 Germall 115 0.10 Lubrajel Oil 14.00

Manufacturing Procedure:

Combine Phase A ingredients in a suitable mixing vessel, Mix until thePhase is uniform. Grind Phase B in a micropulverizer. When Phase B isfree of pigment specks, add Phase B to Phase A with continuous mixing.Mix until the phases are uniform and free of lumps. Homogenize the batchfor 10-15 minutes or as necessary to make Phase A & B smooth andhomogeneous. In a separate vessel combine Phase C ingredients and beginheating to 80-85° C. with good mixing. Begin heating Phase A to 75-80°C. When all phases are at the proper temperatures slowly add Phase C toPhases A & B with continuous mixing. Mix for 15 minutes with the batchcovered to prevent water loss. Begin cooling the batch. Combine Phase Dingredients in a separate vessel. At 50° C. slowly add Phase D to thebatch with continuous mixing. Continue cooling the batch to roomtemperature. At 25° C. remove the batch and store in airtight containersuntil ready for filling. Check the viscosity and Ph of the batch.

Example 45

Hair Dye Base and Shade Formulations Ingredient Dye Base Dk Ash Bn MedAuburn Water 59.78 59.78 59.78 AlkylPolyglucoside 1.75 1.75 1.75 OleicAcid 10.00 10.00 10.00 Nonoxynol-1 0.70 0.70 0.70 Nonoxynol-4 1.23 1.231.23 Ammonium Hydroxide 4.00 4.00 4.00 EDTA (4Na) 0.05 0.05 0.05Erythorbic Acid 0.40 0.40 0.40 Sodium Sulfite 0.10 0.10 0.10 Bio-PDO7.00 7.00 7.00 Heat to 80 C. for 10 min., cooled, q.s., add IPAIsopropanol 99% 5.00 5.00 5.00 Water 10.00 6.06 8.137 100.00p-Phenylenediamine 0.369 Toluene-2,5-Diamine Sulfate 1.763 0.000m-Aminophenol 0.146 0.018 Resorcinol 1.685 0.000 1-Naphthol 0.168 0.047N,N-Bis(2-Hydroxyethyl)- 0.176 0.046 PPD Sulfate4-Amino-2-Hydroxytoluene 0.922 p-Aminophenol 0.461 Ammonium Hydroxideq.s q.s. (q.s. to Ph 10.0) 100.00 100.00 Ph (25 C.) 10.03 Viscosity cps425 380-440 350-390 (20 C.; RVT; #2; 100 RPM)

Example 46

Composition for use before shaving Ingredient Weight Percent EDTA   35%Sodium lauryl sulfate  3.3% Nipagin   20% Nipazol  0.08% Cetyl alcohol 1.8% Carbopol 940  1.4% White wax  0.15% Polysorbate 80    4% Bio-PDO 11.5% Triethanolamine  1.7% Water 21.07%

Example 47

Aftershave Ingredient Weight Percent Isopropanol 30-70% SD alcohol-4010-30% Acetylsalicylic acid  8-22% Carbomer 0.25-1.75% Propylene glycol 2-15% Glycerin  2-15% PEG 1-8% Water q.s. to 100%

Example 48

Shaving cosmetics containing moisturizers Ingredients Weight PercentBio-PDO   50-90% Oils  0.1-30% H2O 0.01-10% Also: H2O    5.0% Glycerin  31.5% 1,3-butylene glycol   20.0% Bio-PDO   20.0% Polyethylene glycol  15.0% Isostearic acid    7.0% Dimethylpolysiloxane    1.0% Perfume   0.5%

Example 49

Stick delivery system Treatment of razor burn Ingredient Weight percentSolvent* Bio-PDO 72% Gelling agent** Sodium stearate  8% Agent***lidocaine  4% Menthol  1% Water 15% *polyhydric alcohol **alkali metalstearate and/or palmitate ***anesthetic, an antihistamine, ananti-inflammatory agent, an antifungal

Example 50

Water-in-oil emulsion Brushless nonlathering shaving cream IngredientWeight Percent Long-chain fatty alcohol* 4-15% Surfactant** 1-10%Wetting agent*** 1-10% Emollient**** 4-20% *lauryl, stearyl, cetyl,myristyl **anionic, nonionic, amphoteric, or quaternarysurfactants/emulsifiers ***glycerol, propylene glycol, sorbitol, orpolyethylene glycol ****□ rabic □ t or mineral oils

Example 51

Shaving cream Ingredient Weight Percent 70% sorbitol  6.19% Bio-PDO 6.19% Stearic acid 22.80% C10-16 fatty acids 19.00% 40% KOH 20.60%Boric acid  0.70% H2O 23.35-26.37% Perfume 1.00-1.17% Allantoin  0.20%Nipagin  0.20% Vegetable oil  3.00%

Example 52

Shaving creams Ingredient Weight Percent A) Stearin and coconut oil40.56% 40% KOH 20.68% 70% sorbitol and Bio-PDO 13.66% H3B03  2.74%Allantoin  2.74% Anesthesin  2.74% Nipagin  2.74% H2O 22.36% B) Stearin  31% Coconut oil   10% 40% KOH 20.48% 70% sorbitol  6.0% Bio-PDO  7.65%H3BO3  0.65% Nipagin  1.0% Allantoin  1.0% Anesthesin  0.74% Perfume 1.0% Dye  0.05% Na alginate  0.07% H2O 20.36%

Example 53

Pre-shave sticks Ingredient Weight Percent A) Glyceryl monooleate 25-70%Sodium stearate  8-25% Bio-PDO  0-50% H2O  1-10% B) Atlas G-3496  61.65%Sodium stearate   15.0% Water   3.0% Perfume   0.35% Bio-PDO   20.0%

Example 54

Liquid shaving compositions Ingredient Weight Percent A) Nonionicsurfactant 60-97% Bio-PDO  2-25% H2O  1-15% B) Glycerol monooleate  77.8% polyoxyethylene (20) sorbitan monolaurate  6.6   H2O     6%Bio-PDO   9.6%

Example 55

Shaving Solution Ingredient Weight Percent Bio-PDO 50-80% Deionizedwater  1-50%

Example 56

Shaving Solution Ingredient Weight Percent Bio-PDO 50-80% Deionizedwater  1-50%

Example 57

Skin Preparation Solution Application to the surface of the skin priorto shaving Ingredient Weight Percent Bio-PDO  10-80% Deionized water 10-80% Imidazolidinyl urea 0.02-4% Methylparaben 0.02-4% Propylparaben0.01-2%

Example 58

Post hair removal skin care lotion Ingredient Weight Percent Deionizedwater q.s. to 100% Aloe vera gel  6-7.4% Soybean oil  6-7.4% Alphalipoic acid  0.2-1.3% Stearic acid  3.5-4.3% Glyceryl monostearate 3-3.7% Bio-PDO  2.5-3.1% Lauramide DEA  1.4-1.6% Vitamin E  0.4-0.5%Hydrocortisone acetate  0.2-0.5% Vitamin C 0.2-0.25% Carbomer 0.2-0.25%Hydroxymethylcellulose 0.2-0.25% Methylparaben 0.2-0.25% Propylparaben0.09-0.1% Polyquaternium-15 0.09-0.1%

Example 59

Transparent shaving gel Ingredient Weight Percent Bio-PDO   15-20%Lubricant/skin conditioners    2-5% Thickener 0.5-0.8% Neutralizer0.5-0.8% Preservative 0.2-0.5%

Example 60

Enzyme-containing toothpastes Ingredient Weight Percent Bio-PDO   20-73 Friction materials   15-50  Thickening agent    1-1.7 Surfactant   1-6  Essence  0.8-1.2 Water    8-35  Saccharin  0.1-0.3 Pigment    0-0.5 PEG  0-6   Biological enzyme 0.01-2   Menthol    0-0.1 Sodium dihydrogenphosphate  0.1-0.5 Titanium dioxide    0-1   Biological enzymestabilizer  0.1-4  

Example 61

Composition for treatment of oral cavity Anti-inflammatory andantibacterial treatment of the oral cavity with toothpaste IngredientWeight Percent Clindamycin 0.01-0.1% Metronidazole 0.01-0.1% Propyleneglycol   5-10%  Sorbitol (70%)   1-10%  Sodiumdimethyl-p-hydroxybenzoate  0.1-0.5%

Example 62

Beautifying toothpaste Ingredient Weight Percent Beautifying agent0.5%-5 Sepiolite 0.25-4% Polyvinylpyrrolidone (PVP) 0.1-2.5% Humectant15%-25% Bio-PDO Adhesive 1%-2.5% Xanthan gum Foaming agent 1.5-2.5%Sodium dodecyl sulfate (SDS) Abrasive/Friction agent 40-50% Calciumcarbonate Essence 1%-1.5% Saccharin 0.1-0.5 Water q.s. to 100

Example 63

Multifunctional health-care toothpaste Treats dental caries, and hasantimicrobial, anti-inflammatory and desensitizing properties.Ingredient Weight Percent Abrasives   30-55   CaCO3, CaHPO4, Al(OH)3 orSiO2 Wetting agent   15-25   Bio-PDO Thickening agent  1.0-1.4  xanthangum Destaining agent (surfactant)  2.0-2.5  Na dodecyl sulfate Polymer 0.1-2.0  Triclosan  0.1-0.3  Chinese medicine ext.  0.1-0.5 Desensitizer  0.2-0.4  Fluoride  0.2-0.8  Saccharine 0.25-0.35 Perfume  0.8-1.2% Water to 100%

Example 64

Dentifrice composition Ingredient Weight Percent Abrasive   5-50% SilicaBinder 0.1-30% Xanthan gum Humectant  10-80% Propylene glycol Surfactant0.1-5%  Alkyl polyglycosides as nonionic

Example 65

Toothpaste Ingredient Weight Percent Calcium carbonate     40-45%Hydroxyethylcellulose     1-1.3% Bio-PDO     22-25% Sodium laurylsulfate    1.8-2% Nipagin  0.09-0.10% Nipasol 0.025-0.30% Protease  0.25-0.50%Sodium acetate  0.15-0.25% Saccharin  0.10-0.15% Flavoring    0.75-1%Water q.s. to 100%

Example 66

Mouthwash for infants A mouthwash for infants contains, for every 100 gor Ml Ingredient Weight Percent Sorbitol 3.00 Glycerol 3.00Methylparaben 0.20 Propyl paraben 0.10 Bio-PDO 4.00 Disodium EDTA 0.10Sodium lauryl sulfate 0.40 Sodium saccharin 0.06 Petitgraine essentialoil 0.02 Tea tree essential oil 0.03 Potassium sorbate 0.20 Sodiumcitrate 0.05 Potassium phosphate 0.10 Citric acid 0.50 CI19140 0.02CI47090 0.01 Water q.s. to 100

Example 67

Aqueous antiplaque oral compositions Mouth rinse comprisingantibacterial ester, arginine derivative, surfactant, humectantIngredient Weight Percent Ethyl lauroylarginate-HCl 0.1 Sorbitol 10.0Glycerin 10.0 Bio-PDO 7.0 Polysorbate-20 0.8 Cocoamidopropylbetaine 0.8Sodium saccharin 0.03 Flavor 0.10 Water q.s. to 100%

Example 68

Prophylactic and therapeutic agent for mouth care Ingredient WeightPercent Binders  0.1-5.0% Na CM-cellulose Foaming components  0.1-5.0%Na lauryl sulfate Antidesiccants 1.0-15.0% Bio-PDO Preservatives0.02-0.5% Me or Pr p-hydroxybenzoate Flavors  0.1-2.0% peppermint oilAbrasives   5.0-25% colloid silica, silica powder Solvents 0.1-90.0%Water 50.0-90.0%  phosphate buffer Ph 6.5-7.5  0.5-3.0% ethanol0.1-50.0% Biologically active components 0.01-8.0% Protamin sulfate 0.1-5.0% Allantoin 0.05-1.0% Sodium fluoride 0.03-3.0% Vitamin PP0.01-5.0% Provitamin B5 0.05-8.0%

Example 69

Antimicrobial compositions Antimicrobial cream or ointment IngredientWeight Percent Glycerol   6% Bio-PDO  5.5% Sodium lauryl sulfate   1%Cetyl alcohol  4.5% Cetyl palmitate   4% Stearic alcohol  4.5% Stearicacid   4% White petrolatum   5% Antimicrobial agent   1% Water 64.5%

Example 70

Oral compositions containing antimicrobial Mouthwashes, Gargles,Dentifrices, Anti-plaque compounds, Oral film dentifrices, Generalantiseptic, Denture cleansing tablets or solutions. Mouth rinse:Ingredient Weight Percent Alcohol   15% Antimicrobial agent 0.05%Flavoring oil  0.1% Bio-PDO   3% Sodium lauryl Me cocoyl taurate  0.3%Sodium citrate 0.08% Citric acid 0.02% Saccharin sodium  0.1% FD&C GreenNo 30.0002%   Water q.s. to 100%

Example 71

Antiseptic mouthwash Ingredient Weight Percent Ethyl alcohol    6-7   Bio-PDO   12-13    Propolis 0.001-0.10  Cinnamic aldehyde 0.003-0.35 Alkyl dimethylbenzylammonium chloride 0.003-0.35  Water q.s. to 100%

Example 72

Composition containing antibacterial agent Ingredient Weight PercentPhenolic antibacterial agent 0.05-5     Disinfecting alcohol   1-40   Gelling agent  0.1-5     Hydrotrope  0.1-30% Bio-PDO  0.1-50% H2O q.s.to 100%

Example 73

Mouthwash composition containing bactericide Manual spray: IngredientWeight Percent Cineole 2.7 Thymol 1.8 Methyl salicylate 1.5 Menthol 1.5Ethoxylated hydrogenated castor oils 10 Shellac 1.0 Bio-PDO 30 Ethanol51.5

Example 74

Liquid Automatic Dishwashing Detergent Ingredients: Wt. % Water 54.30Citric Acid 5.93 Bio-PDO 6.92 Carbopol ™ 934 2.18 NaOH (50%) 5.74 SodiumBorate 0.99 Sodium Citrate 3.96 Sodium Formate 1.98 CaCl 0.10 SodiumXylene Sulfanate (40%) 4.95 EO/PO Block Copolymer 1.98 SodiumPolyacrylate Mn1200 (45%) 9.89 Protease 0.69 Amylase 0.20 LemonEssential Oil 0.20 Total 100.0 Procedure: Combine and stir water H₂O,citric acid and Bio-PDO ™. Add Carbopol ™ to mixture and □ rab untildissolved. Slowly add sodium hydroxide, and thereafter add remainingingredients.

Example 75

Liquid Laundry Detergent Ingredients: Wt. % Linear Dodecyl BenzeneSulfonate 6.93 Coconut Fatty Acid (C12-C18) 7.52 Tergitol 15-S-7 16.83Triethanolamine 7.52 Bio-PDO 10.89 Citric Acid (50%) 6.33 KOH (45%) 9.30Water 33.65 Protease 0.69 Amylase 0.20 Lavendar Essential Oil 0.10 FD&CBlue 1 0.03 FD&C Red 40 0.01 Total 100.0 Procedure: Combine LinearDodecyl Benzene Sulfonate, H₂O, Triethanolamine and Bio-PDO ™, and stirmixture at 70° C. Add Tergitol. Melt the fatty acids and add to the mix.Slowly add KOH, then slowly add the citric acid. Cool mixture below 30°C. Add the enzymes, fragrance and dye.

Example 76

Liquid Laundry Detergent Ingredients: Wt. % C12-C13 Linear Alcohol EO-74.0 Linear Dodecyl Benzene Sulfonate (60%) 14.0 Sodium Laureth Sulfate(60%) 5.0 Sodium Citrate 4.0 Sodium Borate 4.0 Bio-PDO 3.0 Tinopal CBS-X0.1 Protease 0.7 Amylase 0.2 Monethanolamine 0.5 Coconut Fatty Acid(C12-C18) 2.0 Water 62.5 Total 100.0 Procedure: Ingredients werecombined in the following order, allowing each to dissolve/dispersecompletely before adding the next ingredient: water, Tinopal CBS-X,sodium citrate, sodium borate, monoethanolamine, coconut fatty acid,C12-C13 linear alcohol EO-7, linear dodecyl benzene sulfonate (60%),sodium laureth sulfate (60%), protease, amylase, and Bio-PDO ™

Example 77

Hand Dishwashing Liquid Ingredients: Wt. % Bio-PDO 15.35 Linear DodecylBenzene Sulfonate 19.95 Triethanolamine 6.14 Cocamide DEA 10.74 Tergitol15-S-7 4.60 Sodium Laureth-3EO Sulfate (28%) 4.60 Coco Amido PropylBetaine 7.67 Polyquaternium-6 (20%) 3.07 NaCl (25%) 1.53 Sodium XyleneSulfanate (40%) 6.55 Water 19.19 Lemon Essential Oil 0.58 FD&C Yellow 50.03 FD&C Red 40 0.01 Total 100.0 Procedure: Combine all liquidingredients and stir mixture at 70° C. Gradually add Linear DodecylBenzene Sulfonate and stir until dissolved in mixture and mixture isclear. Cool mixture below 30° C. and add fragrance and coloring.

Example 78

Hand Dishwashing Liquid Ingredients: Wt. % Bio-PDO 15.56 Linear DodecylBenzene Sulfonate 20.23 Triethanolamine 6.22 Cocamide DEA 10.89 Tergitol15-S-7 4.67 Sodium Lauryl Sulfate 4.67 Coco Amido Propyl Betaine 7.78Polyquaternium-6 (20%) 3.11 NaCl (25%) 3.11 Sodium Xylene Sulfanate(40%) 3.50 Water 19.45 Lemon Essential Oil 0.78 FD&C Yellow 5 0.04 Total100.0 Procedure: Combine all liquid ingredients and stir mixture at 70°C. Gradually add Sodium Lauryl Sulfate and stir until dissolved andliquid mixture is clear. Gradually add Linear Dodecyl Benzene Sulfonateand stir until dissolved and liquid mixture is clear. Cool mixture below30° C. and add fragrance and coloring.

Example 79

Engine Coolant Ingredient Weight Percent Bio-PDO 30-60 Deionized water36.5-69   Pyrrole compound 0.05-0.22 Polymer 0.60-1.60 Polyacrylic acid0.05-0.20 Sodium benzoate 0.15-0.90 AEO9 purging agent 0.05-0.10Monocarboxylic acid 0.05-0.25 Dicarboxylic salt 0.05-0.25 4-hydroxy Bubenzoate 0.0001-0.0002 Antifoam 0.0001-0.0002 Green dye 0.0001-0.0002

Example 80

Heat transfer liquids with glass corrosion protection Ingredient WeightPercent Bio-PDO   94% Polyacrylic acid <0.5% KOH (50%) <0.3%Tolutriazole <0.2% Benzotriazole <0.1% Sodium molybdate dehydrate <0.1Hydroxyalkylamine   <5% Antifoam 0.004%  Sodium metasilicate  0.2% Waterq.s. to 100%

Example 81

Antifreeze and/or coolant Ingredient Wt, % Bio-PDO 0.1-99.9%3-hydroxypropionic acid salts or esters 0.1-99.9%

Example 82

Anhydrous phosphate-free antifreeze Ingredient Wt, % Bio-PDO    92-98%Borate (as B4O7) 0.16-0.81% Molybdate (as MoO4) 0.13-0.66% Nitrate (asNO3) 0.073-0.36%  Nitrite (as NO2) 0.67-0.33% Tolyltriazole 0.15-0.50%Silicate (as SiO2) 0.014-0.07% 

Example 83

Antifreeze composition for diesel engines Ingredient Wt, % Monobasiccarboxylic acid   0.1-10% Nitrate salt   0.01-10% Nitrite salt 0.001-10% Azole  0.01-5.0% Molybdate 0.001-5.0% Silicone-silicatecopolymer   0.01-10% Poly(vinylpyrrolidone) 0.001-5.0% Bio-PDO q.s. to100% 

Example 84

Aqueous antifreeze coolant Ingredient Wt, % Sodiumpolyacrylate/polyacrylic acid 0.001-10% Nitrate salt 0.001-10% Nitritesalt 0.001-10% Azole 0.001-10% Polysilicate 0.001-10% Phosphate0.001-10% Molybdate 0.001-10% Bio-PDO q.s. to 100

Example 85

Antifreeze-type coolant Ingredient Wt, % Bio-PDO  93% 2-ethylhexanoicacid 3.1% Neodecanoic acid 1.1% Sodium nitrate 0.2% Sodium nitrite 0.4%Tolyltriazole 0.09% 

Example 86

Sealing agents containing antifreeze Ingredient Wt, % Natural rubberlatex 55% Tackifier resin emulsion 15% Bio-PDO ™ 30%

Example 87

Water-based coating materials applicable at freezing point IngredientWt, % Acronal YJ 2730D 45%  Solvent-soluble resin 15%  Bio-PDO 2%Methanol 3% Butoxyethanol 5%

Example 88

Antifreeze foam Ingredient Wt, % Bio-PDO ™ 45% Isopropanol 40%Polyethylene glycol stearyl ether  5% Dichlorodifluoromethane 7.5% Propane 2.5% 

Example 89

Antifreeze for freezing of foods Ingredient Wt, % Ethanol  49% Water48.5%  Polydimethylsiloxane 0.2% Bio-PDO 1.7% Sodium malate 0.3%Glycerin monocaprylate/caproate 0.2% Glycine 0.1%

Example 90

Antifreeze for solid surfaces Ingredient Wt, % Bio-PDO 70.0% Ethanol 5.0% EO/PO copolymer 20.0% Water  5.0% Corrosion inhibitor 0.12%Nonionic surfactant  0.5% Perfume  0.1%

Example 91

Liquid antifreeze for agrochemicals Ingredient Wt, %2,4-dichlorophenoxyacetic acid  43% Sulfonated lignin 1.5% Bio-PDO   2%Aluminum hydroxide gel (10%) 9.0% Hydroxypropyl guar 0.2% Antifoam agent0.1% Water 44.2% 

Example 92

Antifreeze for fuel tanks Ingredient Wt, % Isopropanol 69.95%  Bio-PDO29.95%  Triethanolamine 0.05% Sodium nitrate 0.03% Benzotriazoleaminesalt 0.02%

Example 93

Heat transfer fluid for electrically heated boilers Ingredient Wt, %Bio-PDO   30-55% Sodium phosphate  0.04-0.10% Ammonium molybdate 0.03-0.09% Water q.s. to 100%

Example 94

Concentrate for preparing antifreezes and heat-transfer agentsIngredient Wt, % Phosphoric acid (78%)  2.0-20.0% Triethanolamine10.0-60.0% 2-mercaptobenzothiazole sodium salt  0.1-1.2% EDTA disodiumsalt dihydrate   0.5-1.5% Caprolactam   0.1-3.0 % 1,4-dihydroxybenzene0.001-3.0% Phosphite P-24 0.001-0.005%   Antifoaming agent 0.02-0.03%Dye 0.05-0.06% Butoxyethanol  0.02-0.3% Water 10.0-35.0% Bio-PDO q.s. to100% 

Example 95

Heat transfer fluid for solar installations Ingredient Wt, % Triethyleneglycol 45-98%  Bio-PDO 1-55% Corrosion inhibitors  1-6%

Example 96

Preparation of a non-foaming liquid heat transfer agent Ingredient Wt, %Bio-PDO 96.42%  Sodium salt of poly(acrylic acid) 0.02%  Sodium borate  2% Sodium benzoate   1% Sodium nitrite 0.15%  Sodium nitrate 0.1%Benzotriazole 0.2% Poly(dimethylsiloxane) 0.01%  Sodium silicate 0.1%

Example 97

Heat transfer refrigeration fluid Ingredient Wt, % Bio-PDO 45% Propylenecarbonate  5% H2O 50%

Example 98

Antifreeze composition Ingredient Wt, % Part A Cellulose gum 0.5% Alginic acid 0.5%  Gelatin  2% Water 47% Bio-PDO 50% Part B Ferricchloride  5% Water 45% Bio-PDO 50%

Example 99

Engine Coolant Bio-PDO 49.74%  Water 48.76%  Fluoro-surfactant 0.01%Corrosion inhibitor 1.29% Defoamer 0.08% Dye 0.12%

Example 100 Heat Transfer Composite

The composite comprises Bio-PDO, and/or glycerin, and water as majorcomponents, and contains 0.5-5.0 wt. % of C₈₋₁₂ aliphatic dibasic acidsand the alkali metal salts, 0.5-5.0 wt. % of benzoic acid and the alkalimetal salts, 0.05-1.0 wt. % of triazoles, and 0.01-0.5 wt. % ofthiazoles.

Example 101 Reusable Thermal Pack and Flow Retardant Gel

The thermal pack for therapeutic use includes a gel pad in a 1^(st)flexible sealed bag connected to a pressure chamber from a 2^(nd)flexible sealed bag which can be inflated. The gel comprises clay(bentonite) and Bio-PDO, and includes a fibrous material to prevent flowand increase heat capacity.

Example 102 Non-Aqueous Heat Transfer Fluid

The invention is directed to a heat transfer system comprising a heattransfer fluid. The heat transfer fluid comprising non-buffered Bio-PDO,and at least one Bio-PDO™ soluble additive selected from the groupconsisting of a molybdate salt, a nitrate compound and an azolecompound.

Example 103 Antifreeze Coolant Composition for High TemperatureApplications

The present invention comprises an improved antifreeze coolantcomposition with certain additives (0.01 wt. % to 5.0 wt. %) that serveto increase the thermal stability of the Bio-PDO™ component of aBio-PDO/water (5-95:95-5) coolant composition and to reduce the tendencyof the Bio-PDO component to degrade under elevated thermal conditions.These additives comprise organic compounds with a carboxylic acid moietyand a hydroxyl moiety, and also tricarballylic acid. Another aspect ofthis invention concerns a method for improving the stability of theBio-PDO component of a Bio-PDO/water coolant composition in enginecooling/heating systems by formulating a Bio-PDO/water coolantcomposition with the thermal stability additive to form an improvedcoolant composition, and contacting the engine cooling/heating systemwith the improved coolant composition.

Example 104

Cryopreservation composition of Bio-PDO and a vehicle solution ComponentConcentration Bio-PDO 0.05M to about 6.0M 0.5M to about 4.0M (morepreferred) 0.5M to about 3.0M (most preferred) EuroCollins solution:Sodium (Na+) 10 Mm Potassium (K+) 115 Mm  Chloride (Cl−) 15 Mm Phosphatemonobasic (H2PO4−) 15 Mm Phosphate dibasic (HPO42−) 42.5 Mm  Bicarbonate (HCO3) 10 Mm Glucose 194 Mm 

Example 105

Aircraft Deicing Fluid Ingredients: % Wt. Bio-PDO 92 Water 7.14Polyethylene glycol ether 0.2 EO/PO alkoxylate 0.2 KOH (50% solution).06 Sandocorin 8132C 0.4

Example 106

Aircraft Deicing Fluid Ingredients: % Wt. Bio-PDO 45.5 Water 53.165Tolytriazole 0.4 Silicon anti-foamer 0.2 Potassium Hydroxide .035Triethanolamine 0.3 Sodium arylalkyl sulfonate 0.4

Example 107

Aircraft runway deicing composition Ingredient Wt, % Alkali metalcarboxylate  20-25% Alkali earth metal carboxylate   1-15% Bio-PDO  1-35% Alkali metal phosphate 0.01-1% Alkali metal silicate 0.01-1%Triazole 0.01-1%

Example 108

Aircraft runway deicing composition Ingredient Wt, % Alkali metalcarboxylate     1-40% Alkali earth metal carboxylate     1-25% Bio-PDO    1-35% Alkali metal phosphate   0.01-1% Alkali metal silicate  0.01-1% Triazole   0.01-1% Water q.s. to 100%

Example 109

Deicer/anti-icer for aircraft Ingredient Wt, % Water 41% Bio-PDO 50%Polysaccharide  3% Corrosion inhibitors  6%

Example 110

Deicers for polyurethane foam-lined LPG tanks Ingredient Wt, %Isopropanol 40% Bio-PDO 60%

Example 111 Liquid Carboxylate Deicer Composition

The liquid deicer compounds suitable for roadways, runways, and bridgesinclude: (a) aqueous carboxylate salt of alkali metal, especially asformate, propionate, and/or lactate; (b) corrosion inhibitors forprotection of galvanized steel; (c) auxiliary corrosion inhibitors fornonferrous metals, esp. Al alloys; and (d) optional Bio-PDO. Thecorrosion inhibitor is preferably a polyvalent metal compd., esp. Laacetate hydrate or a mixed lanthanide salt sol. In water, or optionallya Mg-ion compd. And/or a sulfide salt. The deicer optionally includes50-10,000 ppm of tolyltriazole as auxiliary inhibitor for nonferrousmetal surfaces. The typical aqueous deicer contains potassium acetate50%, tolyltriazole 0.15-0.75%, lanthanide nitrate hexahydrate 1.0-3.0%,and trimercaptotriazine tri-Na salt 10.10-0.75%, water q.s. to 100%.

Example 112 Water-Activated, Exothermic Chemical Deicing Formulation

Deicing compositions are provided for removing ice from a surface whichinclude either succinic acid or succinic anhydride, or both, and aneutralizing base such as sodium hydroxide, potassium hydroxide, orammonium hydroxide wherein the deicing compositions when mixed withwater produce succinate salts in a reaction that rapidly releasessufficient heat to melt the ice on the surface and the succinate saltsact as a deicer and freeze point depressant. The deicing compositionsmay further include Bio-PDO which inhibits reformation of the ice on thedeiced surface. The deicing compositions are suitable and effective forairport applications in which corrosion of aircraft alloys and concreterunways are of concern.

Example 113 Anti-Icing Fluid or Deicing Fluid

The title non-electrolytic, non-toxic, biodegradable anti-icing ordeicing composition comprises: (a) water; (b) a non-toxic freeze pointdepressant selected from the group consisting of C2-6 monohydricalcohols, Bio-PDO, mono-Me or Et ethers of C3-12 polyhydric alcohols ormixtures thereof, (c) a nontoxic thickener. The composition is acontinuous single phase liquid that exhibits pseudoplasticity, and isuseful on the surfaces of, for example, aircraft, airport pavements,roadways, walkways, bridges, entrances, structures, canals, locks,components, vessels, nautical components, railroad switches, and motorvehicles. A typical composition contained water, Bio-PDO™ and/orpropanol and xanthan.

Example 114

Animal feed supplement WO9733488A1 Ingredient Weight Percent SodiumPropionate 10% Bio-PDO  5% White Grease 40% Filler 45% (Dairy, fiber,grains, and flavor enhancers)

Example 115

Energetic feed additive Ingredient Weight Percent Bio-PDO 25-48%Glycerol 25-48% Nutritionally suitable acid  1-17% (e.g. C2-C20aliphatic carboxylic acids) Water  1-32% Vitamins & Minerals .0001-4%  

Example 116

Aerosol compositions for animal feeds US2006034978A1 Ingredient WeightPercent Molasses 25% Propylene Glycol 23% Soy Lecithin 10% Water 22%Bio-PDO 4.5% Flavoring 0.5% Isobutane/Propane/Butane  15%

Example 117

Flavored Ink Jet Printing Fluid Ingredient Amount Bio-PDO 94.2% Glycerin 4.0% FD &C Blue 1  1.6% Balls of fire flavor  0.2%

Example 118

Berry Flavor Concentrate Ingredient Amount Bio-PDO 53% Ethanol 10% Water30% Berry flavor  3% Citric acid  4%

Example 119

Edible Pet Chew Ingredient Amount Proteins 5-50% Carbohydrates 20-80% Bio-PDO 5-50% Water 5-30%

Example 120

Low calorie sugar substitute Ingredient Amount Sorbitol 48.34%  Water48.34%  Sodium alginate 0.4% Calcium sulfate 0.3% Guar gum 1.0% Wheatplant fiber 0.5% Bio-PDO 1.0 %  Neotame 0.02%  Potassium sorbate 0.1%

Example 121

Ice cream toppings Ingredient Amount Flavoring agent 0.05-40% Fat0.01-50% Bio-PDO   0.1-40% Sweetener up to 80% Emulsifier up to 10%Water   0-20%

Example 122

Frozen beverage Ingredient Amount Water 60.6 % Bio-PDO 20.2 %Polyethylene 18.3 % Propylene glycol alginate  0.7 % Caramel colorant 0.2 %

Example 123

Flavor delivery system Ingredient Amount Benzaldehyde 20% Polysorbate 8040% Bio-PDO 40%

Example 124

Soft-frozen cocktail drink Ingredient Amount Ethanol  2-15% Bio-PDO12-14% Base flavor mix q.s. to 100%  

Example 125

Flavored micro emulsion for Beverages Ingredient Amount Flavor oil  4.1%Tween-60  4.1% Water 16.5% Bio-PDO 75.4%

Example 126

Food flavoring material Ingredient Amount Glutamate  9.5 g IMP 0.25 gGMP 0.25 g Lactose  5.0 g Sodium 10.0 g chloride Water 60.0 kg Bio-PDO15.0 kg

Example 127

Heat-stable flavoring Ingredient Amount Tamarind seed gum 50 g Bio-PDO50 g Water 200 g  Sodium pyrophosphate  3 g

Example 128

Fried Food Preservative Ingredient Amount Soybean oil 75 parts Lecithin20 parts Bio-PDO  5 parts

Example 129

Non-aqueous Beverage Gel Ingredient Amount Me cellulose  10 partsBio-PDO 100 parts

Example 130

Food Preservation Emulsifier Ingredient Amount Capric acid monoglyceride75% Bio-PDO 15% Water  7% Sodium glutamate  3%

Example 131

Liquid Heat-Setting Confections Ingredient Amount Bio-PDO 17.7% Glycerol monooleate 0.7% Lecithin 0.7% Antioxidant 0.0% Honey 0.1%Coloring 0.3% Flavoring 0.3% Potassium citrate 1.2% Artificial sweetener0.2% Glycerol 53.1%  Starch 23.6%  Carrageenan 2.1%

Example 132

Instant dumplings Ingredient Amount Flour 40-60 parts Potato starch20-30 parts Acetic acid starch 10-20 parts Refined salt  0.5-5 partsEmulsifying agent  0.2-1 parts Sorbitol  2-8 parts Bio-PDO  2-6 parts

Example 133

Grated Cheese Preservative Ingredient Amount Bio-PDO  20 parts Sodiumchloride  18 parts Lactic acid 0.1 parts Propionic acid 0.1 partsSucrose   2 parts Ascorbic acid 0.05 parts  Glycerol monostearate 0.1parts Water 59.65 parts 

Example 134

Edible solid for confectionery coatings or cake or cookie doughIngredient Amount Bio-PDO 80% Nonfat dry milk solid 20%

Example 135

Ready-made/Instant Food Preservative Ingredient Amount Bio-PDO 50 partsAcetic acid  3 parts Sodium acetate 1.5 parts  Ethanol (95%) 105.3parts  

Example 136

Multi-phase delivery system for food supplements and meal replacementsIngredient Amount Creatine monohydrate 16.71%  Glycerol 15.97%  Cornsyrup 21.20%  High-fructose corn syrup 24.78%  Gelatin 5.51% Bio-PDO5.51% Modified starch 2.75% Water 4.96% Other ingredients 2.61%

Example 137

Mulberry Leaf Preservative Ingredient Wt, % Overall Actives  3-8% Phregulator 20-30% Malic acid  1-35% Citric acid 18-25% Sorbic acid 15-20%Hydrochloric acid  8-14% Phytic acid 16-25% Dewatered acetic acid  8-15%Redox agent 20-30% Sodium sulfate 15-25% Potassium sulfate 18-28% Pepsin25-40% Papain  5-42% Moisture activity-reducing agent 20-30% Sodiumpyrophospahte 10- 15%  Sodium chloride  6-10% Bio-PDO  8-15% Agar  5-40%Kara gum 15-25% Gelatin 21-30% Disinfectant 15-25% Josamycin 15-40%Fupaisuan 18-25% Phage 22-30% Lysozyme 20-30% Water q,s, to 100%  

Example 138

Fining product Ingredient Amount Collagen  3-40% Bio-PDO  2-50%Buffering system 0.5-5% Preservative 0.1-5%

Example 139

Semi-moist feed for herbivorous animals Ingredient Amount Gelatinizedstarch 5-55% Sugars 5-80% Bio-PDO  2-8% Water 15-30% 

Example 140

Preservative for bakery products Ingredient Amount Ethanol  1.0% Bio-PDO 0.5% Acetic acid  0.03% Sodium acetate  0.02% Water 98.45% (Sweet riceflour 600 g, water 400 MI and preservative 16 g)

Example 141

Food moistening agent for starch and(or) protein raw materialsIngredient Amount Bio-PDO 40-90% Sorbitol 10-60% (Fish cake (kamaboko)96% and moistening agent 4%)

Example 142

Solid food condiment Ingredient Amount Bio-PDO 1-70 parts Gelatin 10parts Condiment* 80-93% total solids *Catsup, vinegar, apple butter,dried onion flakes, mustard, pickle relish

Example 143

Microbial stabilized cooked dehydrated meat, vegetables, or fruitsIngredient Amount Freeze-dried chicken solids 34.3% Glycerol 32.4% H2O27.8% Salt  0.8% Sugar  1.5% Monosodium glutamate  1.8% Bio-PDO  1.1%Potassium sorbate  0.3%

Example 144

Stable emulsifier for sponge cakes and creams Ingredient Amount Sorbitol(70%) 570 g Bio-PDO 200 g Ethanol 20 g Water 800 g Sucrose monosterate160 g Sodium hydroxide (10%) 16 ml Propylene glycol monostearate 40 gGlycerol monostearate 200 g

Example 145

Fruit coating Ingredient Amount Bio-PDO  5% Water 45% Ethanol 50%

Example 146

Frozen or processed meats coating Ingredient Amount cellulose propionateflake 45 parts acetyl tributyl citrate 55 parts Bio-PDO 5 parts

Example 147

Stabilizer for semidry feeds Ingredient Amount Bio-PDO 51.2% Glycerol35.3% Sorbitol 13.5%

Example 148

Brine solution for freezing fresh foods (fish, meat, vegetable, etc)Ingredient Amount Ethanol  40-60% Bio-PDO   2-20% Preservatives 0.05-1%H2O q.s. to 100%

Example 149

Lycopene pigment Ingredient Amount Lycopene pigment 0.8 g Naturalvitamin E 0.2 g d-limonene 2 g Palm oil 5 g SAIB 6 g Water 60 g Arabicgum 20 g L-ascorbic acid 0.1 g Bio-PDO 10 g

Example 150

Low Calorie Honey Substitute Ingredient Amount CM-cellulose gum  0.500%HPM-cellulose gum  0.500% Xanthan gum  0.223% Propylene glycol alginate0.0525% Sodium bicarbonate  0.131% Glycerin  5.91% Bio-PDO  1.31%Aspartame  0.223% Acesulfame K 0.0421% Food Color Blend  0.237% HoneyFlavor  0.17% Vanilla extract 0.0657% Water  90.7%

Example 151

Fabricated fruit pieces Ingredient Wt % % of Piece Soft Berry Center90.0% Corn syrup  20.3% Blueberry Flavor  1.1% Bio-PDO  52.8% Water 7.2% Modified corn starch  5.4% Modified tapioca starch  5.5% Fructose 4.0% Malic acid  0.7% Citric acid  1.0% Grape skin extract color  1.0%Dried blueberry powder  0.5% Salt  0.5%   100% Thin Film Coating 10.0%Sodium citrate  0.23% Water 76.98% Gellan gum  0.59% Citric acid  0.20%Sucrose  10.0% Grape skin extract color  0.5% Blueberry powder  0.5%Bio-PDO  10.0% Sunflower oil  0.5%   100%

Example 152

Method for producing feed Ingredient Weight Percent Fish meal  70% Wheatpowder  19% Bio-PDO   6% Soybean cake   3% Vitamins   3% Minerals 0.8%Salt 0.4%

Example 153

Agricultural Chemical Suspension Ingredient Weight Percent AmmoniumSulfate 30-70% Bio-PDO 20-80% Igepal ® RC-630  1-9%

Example 154

Liquid and paste automotive cleaner Ingredient Weight Percent Bio-PDO0.5-20% Coco fatty acid alkanolamines 0.8-50% Sodium lauryl ethersulfate 0.5-45% Sodium lauryl sulfate 0.5-40% Dodecylbenzenesulfonicacid   1-50% Cocoamidopropylbetaine   1-35% Coco fatty aciddiethanolamides 0.3-35% Triethanolamine   1-30% Sodium tripolyphosphate0.2-10% Sodium metasilicate 0.5-20% NaCl 0.2-10% MgCl2 0.2-10% NaOH0.2-10% Formaldehyde  0.1-5% Pigments/dyes 0.1-50% Fragrance 0.3-10%

Example 155

Latex Paint Ingredient Weight Percent Water   10-40% Hydroxyethylcellulose 0.2-1.0% Defoaming agent 0.2-1.0% Dispersing agent 0.2-1.0%Mildew-proof and preservative agent 0.2-0.8% Bio-PDO    1-5% Pigment   5-30% Kaolin   10-50% Nanoparticles 0.5-1.5% Silicone 0.5-1.5%Styrene-acrylate copolymer microemulsion   15-45% Film-forming auxiliaryagent   0.5-5% Auxiliary agents' 0.2-1.0%

Example 156

Rainproof Paint Ingredient Weight Percent Acrylic emulsion 23-32Polycarboxylate dispersing agent 0.5-1.2 Antifoam BA-202 0.4-1.0 Bio-PDO1.5-2.5 Preservative LXE 0.1-0.3 KOH (40%) 0.2-0.4 Ester 12 asfilm-forming aid 1.5-2.5 Acrylic polycarboxylate thickener 0.5-1.5Nanoscale SiO2 1.0-3.0 Nanoscale TiO2 0.8-1.8 Titanium dioxide 10-20Calcium carbonate  8-15 Kaolin  8-15 Fluorocarbon resin  5-15 Deionizedwater 10-20

Example 157

Ink jet for printing of food Ingredient Weight Percent Bio-PDO 92%Glycerin  4% Isopropyl alcohol  2% FD&C Blue No. 1  2%

Example 158

Cuttlefish ink mixture Ingredient Weight Percent Cuttlefish ink 15-30%Bio-PDO 15-30% Sweetener 30-60% Ethanol 10-15%

Example 159

Blue writing ink Ingredient Weight Percent Bio-PDO  1-10% Prussian blue1.0-5% Oxalic acid 0.2-5% Dodecylbenzenesulfonate 0.01-2%  Arabic Gum0.1-1% Anticorrosive agents 0.1-1% Water q.s. to 100%

Example 160

Hydraulic-lubricating fluid Ingredient Weight Percent Ethyleneoxide-propylene 27.6%  oxide-glycerol Bio-PDO 16.7%  PEG-600 6.6%Styrene-maleic polyester 5.0% Methylphenylsilicone oil 0.5%Triethanolamine 0.5% Benzotriazole 0.1% NaNO2 0.5% Water 42.5% 

Example 161

Liquid suspension Ingredient Weight Percent Bio-PDO 27.6% Glycerine47.0% Polymeric fatty acid ester  0.2% Dispersing agent  0.2%Polyethylene Oxide (dry)   25%

Example 162

Liquid denitrogenation agent for petroleum oils Ingredient Weightpercent Bio-PDO  5-20% Ethylene glycol 10-30% Propanoic acid 10-20%Malonic acid 20-50% Oxalic anhydride 20-30%

Example 163

Pharmaceutical Composition Ingredient Weight Percent Drug Active (1)0.35% Drug Active (2) 0.28% Phenylephrine hydrochloride 0.28% Methylparaben 0.25% Propyl paraben 0.03% Bio-PDO 7.30% Saccharin sodium 0.09%Citric acid 0.14% Strawberry flavor 0.28% Banana flavor 0.28% Sorbitol(70%) 90.56%  Water 0.14%

Example 164

Pharmaceutical composition Ingredient Weight Percent Polyoxyethylenehydrogenated castor oil 5-50% Azone 0-10% Ginseng extract 0-10% Ginkgoleaf extract 0-10% Collagen protein 0-10% Hyaluronic acid  0-3%Allantoin 0.1-1% Zinc gluconate  0-3% Vitamin C 0.1-1%  Vitamin E0.01-0.1%   Bio-PDO 3-30% Glycerol 3-30%

Example 165

Water-soluble lubricant composite Ingredient Weight Percent Polyethyleneglycol ether   70-90% Water resin    5-15% Leveling agent 0.5-1.5%Bio-PDO 0.5-1.5% Polyethylene wax oxide    1-7% Deionized water  1.5-10%

Example 166

Biocide and antifouling dispersant Ingredient Weight PercentAlkyldimethylbenzylammonium 5.0-45.0%   chloride Dialkyldimethylammoniumchloride 1.0-15% Bio-PDO 10-3.0% Water q.s. to 100%

Example 167

Composition for inhibition of corrosion and deposits in water systemIngredient Weight Percent Oxyethylidene diphosphonic acid 1-58%Alkyldimethylamine oxide 1-26% Bio-PDO 1-30% Water q.s. to 100%

Example 168

Completely biodegradable plastic alloy Ingredient Weight Percent Starch30-60 Poly(vinyl alcohol) 10-35 Ethylene-acrylic acid copolymer 2-5Ethylene glycol  0-25 Polyethylene glycol  0-25 Bio-PDO  0-25Polypropylene glycol  0-25 Sorbitol acetate  0-25 Sorbitol ethoxylate 0-25 Glycerol  0-25 Magnesium hydroxide 2-5 Magnesium borate 0.2-0.4Water 10-20

Example 169 Embryo Transfer of Cryopreserved and In-Vitro FertilizedRabbit Oocytes

Ovulatory oocytes, collected from the oviduct of virgin 13 hours afterinduction of ovulation by HCG injection, can be cryopreserved slowly to−30 degrees C. and plunged directly into liquid nitrogen. A mixture of1.5 M Bio-PDO and 0.1 M sucrose can be used as a cryoprotectant. Afterthawing, the oocytes can be incubated with in-vitro capacitated spermfor 5 h in defined Brackett's medium. Fertilized ova can then becultured for an additional 20 h until the 4-to-8-cell stage is reached.These embryos can be transferred to pseudopregnant recipient rabbitswhich should be ‘asynchronous’ in the sense that they are given aninjection of HCG 30, 24 and 18 h before starting to do the embryotransfer.

We claim:
 1. A food composition comprising 1,3-propanediol and a foodingredient, wherein the 1,3-propanediol comprises at least 3% biobasedcarbon, wherein the food composition is biodegradable and has a loweranthropogenic CO₂ emission profile as compared to a food compositioncomprising 1,3-propanediol with a biobased carbon content of 0%.
 2. Thefood composition of claim 1, wherein the 1,3-propanediol has at least100% biobased carbon.
 3. The food composition of claim 1, wherein the1,3-propanediol is biologically derived through a fermentation process.4. The food composition of claim 1, wherein the 1,3-propanediol has anis ultraviolet absorption at 220 nm of less than about 0.200 and at 250nm of less than about 0.075 and at 275 nm of less than about 0.075. 5.The food composition of claim 1, wherein the 1,3-propanediol has a “b”color value of less than about 0.15 and an absorbance at 275 nm of lessthan about 0.050.
 6. The food composition of claim 1, wherein thecomposition comprises between about 3% to about 98% 1,3-propanediol byweight.
 7. A food composition comprising an ester of 1,3-propanediol anda food ingredient, wherein the 1,3-propanediol comprises at least 3%biobased carbon, wherein the food composition is biodegradable and has alower anthropogenic CO₂ emission profile as compared to a foodcomposition comprising an ester of 1,3-propanediol with a biobasedcarbon content of 0%.
 8. The food composition of claim 7, wherein the1,3-propanediol has at least 100% biobased carbon.
 9. The foodcomposition of claim 7, wherein the 1,3-propanediol is biologicallyderived through a fermentation process.
 10. The food composition ofclaim 7, wherein the ester has the formula R1-C(═O)—O—CH2-CH2-CH2-OH,wherein R1 is a linear or branched carbon chain of a length betweenabout 1 and about 40 carbons.
 11. The food composition of claim 7,wherein the ester has the formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2,wherein R1 and R2 are linear or branched carbon chains of a lengthbetween about 1 and about 40 carbons.
 12. A flavoring agent compositioncomprising 1,3-propanediol and a flavoring ingredient, wherein the1,3-propanediol comprises at least 3% biobased carbon, wherein theflavoring agent composition is biodegradable and has a loweranthropogenic CO₂ emission profile as compared to a flavoring agentcomposition comprising 1,3-propanediol with a biobased carbon content of0%.
 13. The flavoring agent composition of claim 12, wherein the1,3-propanediol has at least 100% biobased carbon.
 14. The flavoringagent composition of claim 12, wherein the 1,3-propanediol is isbiologically derived through a fermentation process.
 15. The flavoringagent composition of claim 12, wherein the 1,3-propanediol has anultraviolet absorption at 220 nm of less than about 0.200 and at 250 nmof less than about 0.075 and at 275 nm of less than about 0.075.
 16. Aflavoring agent composition comprising an ester of 1,3-propanediol and aflavoring ingredient, wherein the 1,3-propanediol comprises at least 3%biobased carbon, wherein the flavoring agent composition isbiodegradable and has a lower anthropogenic CO₂ emission profile ascompared to a flavoring agent composition comprising an ester of1,3-propanediol with a biobased carbon content of 0%.
 17. The flavoringagent composition of claim 16, wherein the 1,3-propanediol has at least100% biobased carbon.
 18. The flavoring agent composition of claim 16,wherein the 1,3-propanediol is biologically derived through afermentation process.
 19. The flavoring agent composition of claim 16,wherein the ester has the formula R1-C(═O)—O—CH2-CH2-CH2-OH, wherein R1is a linear or branched carbon chain of a length between about 1 andabout 40 carbons.
 20. The flavoring agent composition of claim 16,wherein the ester has the formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2,wherein R1 and R2 are linear or branched carbon chains of a lengthbetween about 1 and about 40 carbons.